Enhancement of surface-active solid-phase heterogenous catalysts

ABSTRACT

Surface-active solid-phase catalyst activity may be substantially improved by creating deliberate repetitive surface-to-surface contact between portions of the active surfaces of catalyst objects. While they are immersed in reactant material such contact between portions of the active surfaces of catalyst objects can substantially activate the surfaces of many heterogeneous catalysts. Examples are given of such action employing a multitude of predetermined shapes, supported catalyst structures, etc. agitated or otherwise brought into contact to produce numerous surface collisions. One embodiment employs a gear pump mechanism with catalytically active-surfaced gear teeth to create the repetitive transient contacting action during pumping of a flow of reactant. The invention is applicable to many other forms for creating transient catalytic surface contacting action. Optionally catalytic output of such systems may be significantly further improved by employing radiant energy or vibration.

RELATED APPLICATIONS

This application claims priority under 35 U.S.C. §119(e) to co-pendingU.S. Provisional Application Ser. No. 60/705,656, filed Aug. 3, 2005,the contents of which are incorporated herein by reference.

FIELD OF THE INVENTION

The present disclosure describes heterogeneous catalysts and catalystreactor systems and related methods, which employ surface-activesolid-phase catalyst materials acting on reactant matter.

BACKGROUND OF THE INVENTION

Catalyst materials promote chemical reactions but do not themselvesenter into the output product nor are they consumed by the reaction.“Heterogeneous catalysis” refers to a catalytic process in which thephysical states of the catalyst and reactant (material involved in thechemical reaction) are different. This is distinguished from“homogeneous catalysis”, where the reactant and the catalyst have thesame physical state and, as a result form solutions or miscible mixtures(liquid/liquid; gas/gas). For example, the physical state ofheterogeneous catalyst material may typically be solid-phase (e.g., ametal or ceramic) while the reactants may be gases and/or liquids.Therefore, the “surfaces” of a solid catalyst material that may contacta reactant play a significant role in catalysis.

However, with advancing knowledge of the nature of “states of matter”many conventional theoretical models of solid, liquid or gas may bepoorly suited to describe the range of states of matter. A “surface”displays far more complexity than an oversimplified image of a visualplane used in many conventional models to describe it. The theoreticalmodel of a sharp boundary as characteristic of a surface may bemisleading for understanding certain catalytic surface activity.Instead, a surface of a solid may be viewed as a zone or transitionregion where close spaced atomic groups inside the solid taper off asthe view looks toward the edge of the surface zone. Inside, the solidcomponents are closely bound but at the surface such bonding isdisturbed.

For more than a century, countless specific examples of catalysts havebeen cataloged, developed and applied. The many known reactionspresently form the foundation of most of the world's chemical industry.Recognition of catalytic effects began at the dawn of the 19^(th)century. In the early 20^(th) century, many large industrial scalereactions began utilizing important industrial processes usingheterogeneous catalysts. Notable examples are the Haber-Bosch ammoniasynthesis (fertilizers for world agriculture), the Fischer-Tropschhydrocarbon synthesis (oil, gasoline and hydrocarbon materials), and thesynthesis of plastic materials, resulting in a vast polymer chemicalindustry. Catalytic processes in the chemical industries of the worldcurrently have enormous commercial significance. A large fraction of allchemical production is catalyst based. Some approaches to fundamentaltheories of catalysis exist, such as the Density Functional Theory,which involves mathematical approximation of some quantum-mechanicalfactors representing chemical bonding. Nevertheless, development ofproducts and processes remain largely based on pragmatic experimentalapproaches. Consequently, the field of heterogeneous catalysis isreplete with “recipes” for producing various kinds of catalystsutilizing a wide variety of materials and constructions. In fact,catalysts are often known by the molecular species of their reactionsrather than by their mode of action or even by their construction. Threetypical examples of recent U.S. patents involving catalysts are: U.S.Pat. No. 6,821,922 to Tacke et al “Supported Catalyst For The ProductionOf Vinyl Acetate Monomer”; U.S. Pat. No. 6,852,669 to Voit et al“Hydrogenation Catalyst”; and U.S. Pat. No. 6,867,166 to Yang et al“Selective Adsorption Of Alkenes Using Supported Metal Compounds”. Aproduct descriptive brochure from the Johnson Matthey Company, a majorsupplier of catalyst materials, is similarly functionally descriptivefor each of a group of Palladium based products the company offers forcarbon-carbon bonding. (See brochure available on the Internet atwww.amcpmc.com/pdfs/producttype/45.pdf). In short, the chemist'sunderstanding of the foundational fundamentals of catalyst artprogresses but as yet is incomplete.

Heterogeneous catalysts having a spherical particle shape have oftenbeen employed as catalysts and catalyst substrates. Such interest hastypically been in pursuit of large apparent surface area for contactwith reactant, with some added concern for thermal properties such asheat transfer in exothermic reactions. For example, U.S. Pat. No.6,747,180 to Ostgard et al, “Metal Catalyst” describes the forming ofhollow metallic spheres of 0.5 mm to 20 mm diameter. Its focus appearsto be reduction of the amount of expensive metal unavailable in thesphere's interior to the catalytic surface of the desired sphericallyshaped particles.

U.S. Pat. No. 5,237,019 to Weiland et al, describes small sphericalparticles of from 0.01 to 3.0 mm diameter composed of organosiloxanematerials containing platinum group metals. The particles are specifiedto have a bulk density below that of water while allowing a wide rangeof surface area to be obtained from varied particle size. Obtaininglarge surface area this way appears a major objective. Emphasis is alsoplaced on the character of the catalyst metal dispersed in of suchcompositions.

U.S. Pat. No. 6,518,220 to Walsdorff et al, describes “Shaped Catalysts”of a hollow cylindrical or annular form of a catalytically activematerial. Improved selectivity of the preferred shape as well as reducedpressure drop are the disclosed objectives of the design.

In several U.S. patents to Wang et al (U.S. Pat. Nos. 4,804,796,4,701,436 and 4,576,926), hollow spheres are disclosed that are formedin various ways to enable the effective density of such spheres to bemade to allow such to float in a medium of choice. An object of thesepatents is to improve the dispersion of such catalyst in the selectedreactant medium.

U.S. Pat. No. 3,966,644 to Gustafson, titled “Shaped Catalyst Particles”describes a longitudinally symmetric trilobe shaped alumina compositecatalyst particle having a narrow range of sizes and specific porositycharacteristics claimed useful for hydrocarbon conversions of petroleumresiduum. The shape is discussed in terms of its void ratio and flowproperties, improved activity, claimed longer duration of effectiveoperating time and, superior crush resistance.

U.S. Patent Application US 2005/0130837 by Hoek et al, titled “ShapedCatalyst Particles For Hydrocarbon Synthesis” describes a trilobularextruded shaped catalyst form, having a void ratio in excess of 50%,well in excess of the 43% or so of other trilobal designs. Flow ratesappear to be a principal concern of these applicants.

U.S. Pat. No. 4,293,445 to Shimizu et al “Method For Production ofMolded Product Containing Titanium Oxide” discloses the addition a smallproportion of barium for improving the strength of the ceramic catalystproduct.

A focus of conventional improvements in the catalyst art has been tomaximize the surface area of catalyst material exposed to the reactant.This has been accomplished via various means: in one way throughcreation of powdery and porous materials; in another through highsurface area geometries; in another through the use of chemicalprocesses acting on the catalyst's surface to “activate” or “refresh”it.

Certain investigators outside the field of chemistry and catalysis haveobserved what they believed to be detrimental effects of surface-surfacecontact in the context of electrical switches and relays. Such phenomenawere studied in a series of papers coming from The Bell Laboratories inthe early 1950s (See, The Bell System Technical Journal, May 1958 pp738-776, “Organic Deposits on Precious Metal Contacts” By H. W. Hermance& T. F. Egan). The Bell Labs workers' motivation for the study came fromexamining the intermittent failure of telephone exchange switchingrelays caused by accumulation of organic deposits formed on theircontacts.

Surprisingly this problem was exacerbated when efforts were made tohermetically seal a very large number of switching relays employed in atelephone exchange of that era. The sealing effort initially seemeddesirable to protect the contacts from dust and airborne contaminants.However, small amounts of organic vapor inside the sealed relays (comingfrom magnet wire, insulation, and other organic material of theirfabrication) were not eliminated and deposited on the contacts sealedinside. The resulting problems were severe because the “open” circuitcaused by a deposit would soon disappear, making it difficult to locate.The Bell researchers devised non-current carryingrelay-contact-operating mechanisms to evaluate various kinds of contactmaterial and environments. The signal circuits that appeared mostvulnerable carried essentially no current through the relay contacts andoperated only with very small signal voltages. Such “dry circuit”operation could provide no arcing actions that might clean contacts. TheBell Labs researchers discovered that the carefully chosen corrosionresistant group 10 (platinum group) contact metals were very prone toforming the disturbing organic deposits they named “contact polymers.”

While much effort has been directed to increasing catalysts' effectivesurface area as determined by gas adsorption tests, the resultingincrease in surface complexity and porosity has also led to detrimentalreactant trapping and retarded movement of reaction materials.Accordingly, improved heterogeneous catalysts, catalyst systems andcatalytic reaction methods are still needed.

SUMMARY OF THE INVENTION

The present invention involves, in certain embodiments, utilization ofrepeated catalyst-to-catalyst surface contact to excite catalyticactivity of the contacting surfaces. Previous research has shown suchcontacting can produce surface defects and rearrangement of constituentatoms on contacting surfaces. The applicability and utility of thisphenomena appears to be previously unrecognized and unapplied in thefield of catalysis. As discussed below, such surface-to-surface contactmay be utilized to enhance catalytic activity.

The present invention provides catalytic reactor systems comprising atleast two catalytic objects each object having at least one surfacecomplementary in shape and/or contour to at least one surface on anotherof the catalytic objects such that a projected contact area between twoof the catalytic objects is capable of being greater than 1% of a totalcatalytically active external contact surface area of the two contactingcatalytic objects, and a contact-inducing device configured and arrangedto repeatedly bring complementary surfaces of the at least two catalyticobjects into contact with each other such that the a projected contactarea between two of the contacting catalytic objects is on averagegreater than 1% of the catalytically active total external contactsurface area of the two contacting catalytic objects.

In one embodiment, the catalytic reactor system comprises at least twocatalytic objects each object having at least one surface complementaryin shape and/or contour to at least one surface on each other of thecatalytic objects such that a projected contact area between any two ofthe catalytic objects is capable of being greater than 1% of acatalytically active total external contact surface area of the twocontacting catalytic objects. In another embodiment, each of the twocatalytic objects comprises at least one essentially planar surface suchthat an essentially planar surface of a first catalytic object iscapable of contacting an essentially planar surface of a secondcatalytic object.

Catalytic objects of the present invention may comprise a catalyticallyactive material comprising a metal or metal alloy. Catalytic objects ofthe present invention may further comprise a support material coatedwith a catalytically active material. In one embodiment, the supportmaterial is a ceramic. In another embodiment, the at least two catalyticobjects comprise discrete particles or pellets. In another embodiment,the catalytic objects are essentially non-porous.

In one embodiment, the catalyst reactor system comprises an industrialscale slurry bubble column reactor and the contact-inducing devicecomprises a device configured to generate fluid flow capable ofsuspending and/or agitating the discrete particles or pellets. In oneembodiment, the catalyst reactor system comprises an industrial scalecontinuously stirred tank reactor wherein the contact-inducing devicecomprises a stirring device. In some embodiments, the contact-inducingdevice comprises a mechanical apparatus comprising or to which isattached at least one of the catalytic objects.

In one embodiment, the catalyst objects are discrete particles orpellets having a shape that is essentially a truncated icosahedron. Inanother embodiment, at least one of the catalytic objects has a shapethat is essentially a cylinder. In another embodiment, a cross-sectionof the cylinder perpendicular to its longitudinal axis has a perimeterthat is polygonal. In another embodiment, at least one of the catalyticobjects is configured as a gear having a plurality of gear teeth.

In certain embodiments, the catalyst reactor system further comprises areactor comprising an inlet configured to allow a reactant to flow intothe reactor and an outlet configured to allow a product to flow out ofthe reactor, wherein the catalytic objects are contained within thereactor such that the catalytic objects are exposed to the reactant.

Another aspect of the present invention provides a method for performinga reaction catalyzed by a heterogeneous catalyst, comprising acts of:exposing at least two objects each object having at least one surfacecomplementary in shape and/or contour to at least one surface on anotherof the objects, at least one of which objects is a catalytic objecthaving a surface that is catalytically active, to an environmentcomprising a selected reactant; creating repeated contact between theobjects such that a projected contact area between complementarysurfaces of two contacting objects is on average greater than 1% of acatalytically active total external contact surface area of the twocontacting objects; and allowing the predetermined reactant to undergo achemical reaction at the at least one catalytically active surface toproduced a desired product.

In one embodiment, each of the objects is a catalytic object having asurface that is catalytically active. In another embodiment, each of thecatalytic objects comprises at least one essentially planar surfacehaving an area comprising at least about 1% of the catalytically activeexternal surface area of the object.

In some embodiments, the catalyst objects are immersed in theenvironment. In one embodiment, the environment is a solution comprisingthe predetermined reactant. In another embodiment, the environment is agas comprising the predetermined reactant.

In some embodiments, the contact is recurring and transient. In someembodiments, the contact causes at least a portion of an externalcatalytically active surface area of the catalytic object to becomeregenerated.

The present invention also relates to catalytic objects comprising anexternal surface comprising a plurality of mosaic patches/facets whereinat least one mosaic patch/facet meets an adjacent facet at an edge toform a predetermined three-dimensional shape, wherein at least onemosaic patch/facet comprises a catalytically active material.

In one embodiment, an individual mosaic patch/facet has a surface areagreater than 1% of the total external surface area of the catalyticobject. In another embodiment, each mosaic patch/facet comprises acatalytically active material. In some embodiments, at least one mosaicpatch/facet is essentially planar. In some embodiments, each mosaicpatch/facet is essentially planar.

In one embodiment, the catalytically active material comprises a metalor metal alloy.

In one embodiment, the predetermined three-dimensional shape isessentially a truncated icosahedron. In another embodiment, thepredetermined three-dimensional shape is essentially a cylinder. Inanother embodiment, the predetermined three-dimensional shape isessentially in the form of gear teeth on a gear.

In some embodiments, the edge where two adjacent mosaic patches/facetsmeet is rounded.

Some embodiments of the catalyst object further comprise a supportmaterial coated with the catalytically active material. In oneembodiment, the support material is a ceramic.

The present invention also relates to catalytic reactor systemscomprising a mechanical apparatus constructed and arranged tointermittently create contact between a catalytically active surface ofa catalyst object and a contact surface of a second object, such that aprojected contact area on average between the two objects is greaterthan 1% of the total external contact surface area of the two contactingobjects. In one embodiment, the contact surface of the second object isa catalytically active surface. In some embodiments, the mechanicalapparatus comprises a motor. In some embodiments, the mechanicalapparatus comprises a gear pump device. In some embodiments, themechanical mechanism comprises a series of gear pump devices.

The present invention also provides methods for producing catalyticaction upon at least one reactant material, comprising: providing atleast two catalytic objects, wherein the catalyst objects each comprisea catalytically active material on at least a portion of an externalsurface; exposing the catalytic objects to an environment comprising thereactant material; producing motion of the catalyst objects sufficientto cause repeated frequent transient surface to surface impactingcontact events between external surface areas of the catalyst objectsusing a contact-inducing device, the contact events each having onaverage a projected contact area larger than 1% of the average totalprojected contact surface area of the catalyst objects coming intocontact during the contact event; and transforming at least somereactant material into a desired product chemically different from thereactant material.

In one embodiment, the repeated frequent transient surface to surfaceimpacting contact events progressively occur such that essentially allthe catalytically active external surface of the catalyst objects comesinto contact during the method. In another embodiment, the motionaverages distribution of the contact events over essentially all thecatalytically active exterior surfaces of all the objects.

In one embodiment, the motion averages distribution of the contactevents over a majority of the catalytically active exterior surfaces ofthe objects. In another embodiment, the motion averages distribution ofthe contact events over limited portions of the external surfaces of theobjects comprising the catalytically active surfaces.

In one embodiment, the catalytically active external surface of at leasta portion of at least one catalyst object is segregated into mosaicpatches/facets, each mosaic patch/facet having an exterior surface areathat is substantially less than the total catalytically active externalsurface area of the at least one catalyst object. In one embodiment, afirst mosaic patch/facet of the catalyst object which is segregated intomosaic patches/facets has a composition of surface material differentfrom a second mosaic patch/facet on the same catalyst object. In anotherembodiment, a first mosaic patch/facet of a first catalyst object whichis segregated into mosaic patches/facets has composition of surfacematerial different from a second mosaic patch/facet on a second catalystobject which is segregated into mosaic patches/facets.

In one embodiment, the aspect ratio of at least one catalytic object isless than about 1.05. In another embodiment, the aspect ratios of eachof the catalytic objects is between about 1.25 and about 1.05. Inanother embodiment, the aspect ratio of at least one of the catalyticobject is between 1.25 and 2.00. In another embodiment, the aspect ratioof at least one of the catalytic objects is between about 2.00 and about3.00. In another embodiment, the aspect ratio of at least one of thecatalytic object is greater than about 3.00.

In one embodiment, all the catalytic objects have essentially the sameshape and size.

In one embodiment, all the catalytic objects have essentially the sameshape but differ by more than 5% from at least one other catalyticobject in size.

In certain embodiments, the external surface of the catalytic objectscomprise mosaic patches/facets, and wherein at least a first and asecond catalytic objects have different polyhedral shapes from eachother. In a particular embodiment, the first catalytic object differs bymore than about 5% in size from the second catalytic object.

In some embodiments, the external surface of the first catalytic objectcomprises a first number of mosaic patches/facets while the externalsurface of the second catalytic object comprises a second number offacets. In a particular embodiment, the first catalytic object differsby more than about 5% in size from the second catalytic object.

In one embodiment, a shape of the catalytic objects is substantially thesame as a truncated icosahedron having rounded edges joining adjacentessentially planar mosaic patches/facets, wherein the width of a roundededge, defining a minimum distance separating adjacent essentially planarmosaic patches/facets, does not exceed about 2% of the nominal overalldiameter of the truncated icosahedron.

In one embodiment, the sizes of corresponding dimensions of any twocatalyst objects are within 5% of each other.

BRIEF DESCRIPTION OF THE DRAWINGS

The accompanying drawings are schematic and are not intended to be drawnto scale. In the figures, each identical, or substantially similarcomponent that is illustrated in various figures is typicallyrepresented by a single numeral or notation. For purposes of clarity,not every component is labeled in every figure, nor is every componentof each embodiment of the invention shown where illustration is notnecessary to allow those of ordinary skill in the art to understand theinvention. In the drawings:

FIG. 1 (prior art) is a plot representing the change of state occurringwhen two components A and B link chemically with some possible changesin energy occurring;

FIG. 2 shows a perspective view of a Truncated Icosahedron;

FIG. 3 shows a perspective view of a geometrically ideal TruncatedIcosahedron;

FIGS. 4A and 4B show a view of all thirty-two faces of a TruncatedIcosahedron laid flat and adjoining (FIG. 4B) showing relationship offaces;

FIG. 5 shows the shape of softened TICO facet edges of a TruncatedIcosahedron (e.g. as shown in FIG. 2 or FIG. 3);

FIG. 6 shows a cross-sectional view of a tilted Truncated IcosahedronTICO facet plane, intersecting the mold parting face (parting line);

FIG. 7 shows an exploded and internal view of basic gear pump mechanismcomprising a gear having gear teeth comprising a catalytically activematerial according to one embodiment of the invention;

FIGS. 8A and 8B show a nine-sided cylindrically symmetric catalystsubstrate pellet according to one embodiment of the invention;

FIG. 9 illustrates a geometric hecatohedron;

FIGS. 10A and 10B show a dome design for nine-sided cylindrical catalystpellet ends;

FIG. 11 shows a cross-sectional view of a star roller catalytic objectin a cylindrical reactor chamber according to an embodiment of theinvention;

FIGS. 12A-12C show a cross-sectional view (FIG. 12A) and top views(FIGS. 12B and 12C) of an anvil/striker catalytic object reactor testapparatus according to an embodiment of the invention;

FIG. 13 shows an anvil/striker catalytic reactor test apparatusaccording to one embodiment of the invention;

FIGS. 14A-14C show various views of an anvil portion of theanvil/striker catalytic reactor apparatus of FIG. 13;

FIGS. 14D-14E show close-up views of the anvil apparatus of FIGS.14A-14C;

FIGS. 15A-15B show views of a striker and striker suspension portion ofthe anvil/striker catalytic reactor test apparatus of FIG. 13;

FIG. 16 shows a process flow diagram of a catalytic reactor andanalytical system including the anvil/striker catalytic reactor testapparatus of FIG. 13 used for performing Examples 6-15;

FIGS. 17A-C show a PIN link air-bearing assembly the anvil/strikercatalytic reactor test apparatus of FIG. 13 of;

FIG. 18 is a graph showing the mass numbers and abundance of species inthe product gas for (a) an “unstruck” portion of a Pd anvil and (b) a“struck” portion of a Pd anvil, sampled at various times during a testrun of the anvil/striker catalytic reactor test apparatus of FIG. 13, at70° C.;

FIG. 19 is a graph showing the mass numbers and abundance of species inthe product gas for (a) an “unstruck” portion of a Pd anvil and (b) a“struck” portion of a Pd anvil, sampled at various times during a testrun of the anvil/striker catalytic reactor test apparatus of FIG. 13, at150° C.;

FIG. 20 is a graph showing the mass numbers and abundance of species inthe product gas for (a) an “unstruck” portion of a Pd anvil and (b) a“struck” portion of a Pd anvil, sampled at various times during a testrun of the anvil/striker catalytic reactor test apparatus of FIG. 13,wherein the temperature is lowered from 71° C. to 31° C.;

FIG. 21 is a graph showing the mass numbers and abundance of species inthe product gas for (a) an “unstruck” portion of a Pd anvil and (b) a“struck” portion of a Pd anvil, sampled at various times during a testrun of the anvil/striker catalytic reactor test apparatus of FIG. 13,wherein the temperature is raised from 60° C. to 80° C.;

FIG. 22 is a graph showing the mass numbers and abundance of species inthe product gas for (a) an “unstruck” portion of a Pd anvil and (b) a“struck” portion of a Pd anvil, sampled at various times during a testrun of the anvil/striker catalytic reactor test apparatus of FIG. 13,wherein the temperature is raised from 30° C. to 92° C.;

FIG. 23 is a graph showing the mass numbers and abundance of species inthe product gas for (a) an “unstruck” portion of a Pd anvil and (b) a“struck” portion of a Pd anvil, sampled at various times during a testrun of the anvil/striker catalytic reactor test apparatus of FIG. 13,wherein the temperature is raised from 100° C. to 200° C.;

FIG. 24 is a graph showing the mass numbers and abundance of species inthe product gas for (a) an “unstruck” portion of a Pd anvil and (b) a“struck” portion of a Pd anvil, sampled at various times during a testrun of the anvil/striker catalytic reactor test apparatus of FIG. 13,wherein the temperature is lowered from 85° C. to 40° C.;

FIG. 25 is a graph showing the mass numbers and abundance of species inthe product gas for (a) an “unstruck” portion of a Pd anvil and (b) a“struck” portion of a Pd anvil, sampled at various times during a testrun of the anvil/striker catalytic reactor test apparatus of FIG. 13,wherein the temperature is raised from 24° C. to 130° C.; and

FIG. 26 is a graph showing the mass numbers and abundance of species inthe product gas for (a) an “unstruck” portion of a Pd anvil and (b) a“struck” portion of a Pd anvil, sampled at various times during a testrun of the anvil/striker catalytic reactor test apparatus of FIG. 13,wherein the temperature is lowered from 100° C. to 65° C.

DETAILED DESCRIPTION DEFINITIONS

As used herein, “contact” in the context of catalytic objects or othersolid phase surfaces refers to an intimate meeting, on an atomic basis,of at least some surface material substance of each of two, generallysolid-phase, different meeting bodies. Such contact may transfermaterial between the meeting bodies and/or at least reposition somematerial on one or both bodies.

This disclosure brings new specific meaning to the word “contact.”Typically, the term “contact” in the catalyst arts generally is usedonly in the context of bringing some reactant together with some solid(often a catalyst) upon which some reaction follows.

The present invention introduces a broad range of inventive embodimentsof a potent, fundamental surface-active catalyst enhancement involvingdefined and very specific kinds of contact.

“Solid-phase” refers to matter in the solid-state, i.e., in solidassociation substantially maintaining its inter-atomic configuration;neither liquid nor gas.

“Catalyst object” or “catalytic object” refers to a discrete physical,substantially solid-phase object having an external surface possessingsome catalytic properties when present in some specified environmentdesignated for its use.

“External surface” or “exterior surface” of an object refers to allboundary points between the material substance of a generallysolid-phase object and all surrounding points in space that touch theobject but do not coincide with any material that remains joined to theobject.

“Surface zone” of a generally solid-phase object refers to a regionrelative to its external surface, influencing the object's catalyticactivity, which extends from at least several microns interior to thatsurface to least several microns exterior to it, understanding that suchboundaries are somewhat diffuse.

“Surface-active catalyst” refers to the majority of catalytic action ofsuch a physical catalyst object occurring within or upon a surface zoneof such catalyst object.

“Contact event” or “contacting event” refers to the occurrence of anindividual contact for at least some finite period of time that may beonly of extremely brief duration.

“Separation event” refers to the parting of an existing contact of atleast a minimum separation distance of two microns and, for a finiteperiod of time greater than one microsecond.

“Open time” refers to the time elapsed from a separation event to thenext occurring contact of either separated contact surface.

“Contact condition” refers to contact occurring in one or many instancesduring a defined time period.

“Average contact duty cycle” refers to the ratio of average closed timeto the average time between recurrences of contact for any definedparticular contact condition, or for a defined set of contact events.

“Impacting contact event” refers to the occurrence of a contact eventthat produces an effect on more than one atom of at least one of thecontacting objects either transferring atom(s) between meeting surfaces,or at least two atoms becoming repositioned in at least one catalystobject's surface.

“Projected contact area” refers to the maximum possible area of contactduring a contact event, defined as the area included within thecoincident boundaries of contact between the two contacting surfaces asif completely merged into one another. Such a projected contact area istherefore typically larger than the actual area of all minutematerial-to-material physical contact occurring within that area.

“Total external contact surface” refers to the sum of all possibledifferent projected contact areas of a defined pair of contactingobjects, such as surface-active catalyst objects, or of a defined set ofsuch objects.

“TICO” is an aphorism for a catalyst substrate form that has a shapemodified slightly from a classical truncated icosahedron.

The present invention relates in certain aspects to catalyst reactorsystems configured for creating contact between surfaces, for examplecatalytically active surfaces, of catalyst objects (e.g., solid-phaseheterogeneous catalysts) and methods for fabrication and use of suchcatalysts and catalyst reactor systems. The present invention maycomprise recurring transient catalyst surface interactions. The presentinvention also relates, in certain embodiments, to new geometries forcatalysts, e.g. particulate and/or pelleted catalysts (e.g. asillustrated in FIGS. 2-6 and 8-10), and to novel movement and deploymentof catalytically active surfaces to optimize the amount and frequency ofsurface-to-surface contacting action. In some cases, a substantialmajority of the active surface area of the catalyst objects may beemployed. Catalysts and catalytic methods of the present invention mayincrease catalytic productivity and may also increase the transport ofthe heterogeneous reacting materials, e.g. gases, liquids, slurries,and/or supercritical fluids, through the catalyst surface zones,relative to other known catalysts and catalytic methods.

In one embodiment, the present invention relates to catalytic reactorsystems comprising at least two catalytic objects having complementarysurfaces such that a projected contact area between the two catalyticobjects is on average greater than 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%,10% or more of the catalytically active total contact surface area ofthe catalytic objects, and a contact-inducing device configured andarranged to bring the at least two catalytic objects into contact witheach other. As used herein, “complementary surfaces” may refer to thesurfaces of any two objects (e.g., catalytic objects), or portionsthereof, having a shape, surface topography, and other characteristicsthat allow a projected contact area defining intimate contact betweenthe two surfaces to be substantially coextensive with the entirety ofthe external areas of the surfaces or portions. Examples ofcomplementary surfaces include two essentially planar surfaces; anessentially conical projection and an essentially conical indent (forsame-sized cones); an essentially hemispherical bump and an essentiallyhemispherical indent (for same-sized hemispheres); etc. In oneembodiment, a catalyst reactor system of the present invention comprisescatalytic objects each comprising at least one essentially planarsurface such that the essentially planar surface of a first catalyticobject is capable of contacting an essentially planar surface of asecond catalytic object. The catalytic object may comprise acatalytically active material over at least a portion or overessentially the entirety of its external surface. In certainembodiments, the catalytic object may comprise a support material atleast partially coated by a catalytically active material.

As used herein, a “contact-inducing device” refers to any apparatuscapable of bringing the catalyst objects into repeated contact with eachother. In some embodiments, the contact-inducing device may be anagitation system of a reactor in which the catalytic objects are placed,such as a slurry flow generating apparatus of an industrial scale slurrybubble column reactor or an impeller of an industrial scale continuouslystirred tank reactor, for example. In certain embodiments, thecontact-inducing device is a mechanical motor-driven apparatus which isconfigured to physically position the surfaces of at least two catalystobjects in contact with each other. In certain embodiments, a catalyticreactor system may comprise a mechanical mechanism for placing at leasttwo catalyst objects in contact, such that a projected contact areabetween the two catalytic objects is greater on average than about 1% ofthe catalytically active total external contact surface area of thecatalytic objects. In certain such cases, the mechanical mechanism maybe a gear pump, a series of gear pumps, or the like, and the catalystobjects may be in the form of rotatable gears, or teeth thereof, orrollers which are arranged to be in contact with each other and/or othersurfaces. FIG. 7 shows an exploded and internal view of basic gear pumpmechanism, while FIG. 11 illustrates a catalytic roller assembly.

Catalyst or catalytic objects of the present invention may comprise aplurality of facets, or equivalently “mosaic patches,” wherein at leastone facet meets an adjacent facet at an edge to form a three-dimensionalshape, wherein at least one facet comprises a catalytically activematerial. In some cases, an individual facet has a surface area greaterthan 1% of the total external surface area of the catalytic object. Insome embodiments, a facet, or portions thereof, may comprise acatalytically active material. The edges where the facets meet may beessentially straight edges or edges which may be altered (e.g.,rounded). The facets may have surfaces that are essentially planar ornon-planar. It is advantageous if the surface contours of facets ofcatalyst objects to be brought into contact are complementary, asdefined above. Faceted catalytic objects may comprise, in certainembodiments, particulate or pelleted forms having, in certainembodiments, particle sizes typical of those known in the art forparticulate catalysts. For example, particle sizes may be in the rangeof 0.1 mm-25 mm, more typically from 1 mm-10 mm. These catalytic objectsmay be particularly well suited for use in industrial scale reactors,such as slurry bubble column reactors, fluidized bed reactors,continuously stirred tank reactor.

The shape of the catalyst objects may vary upon a particularapplication, as described in further detail below. Examples ofpotentially suitable shapes include, but are not limited to,polyhedrons, such as a truncated icosahedron, cylinders, gears (e.g.,gear having gear teeth), etc.

The present invention also describes methods for performing reactionscatalyzed by a heterogeneous catalyst. Such methods may comprises actsof exposing at least two catalytic objects, at least one of which hassurfaces that are catalytically active, to a defined environmentcomprising a selected reactant; creating contact between the catalystobjects such that a projected contact area between the two catalyticobjects is greater on average than 1% of the catalytically active totalexternal contact surface area of the catalytic objects; and allowing theselected reactant to undergo a chemical reaction at a catalyticallyactive surface to produce a desired product. In certain embodiments, thecatalyst objects are immersed in and surrounded by the environment,which may be a solution or pure material in liquid or gas formcomprising the predetermined reactant, for example. In certainembodiments, methods of the present invention comprise contacting thecatalyst objects in a recurring and transient manner. In some cases,this may result in enhanced performance of the catalyst (e.g, higheryields).

In certain cases, the recurring and transient contact between catalyticobjects may advantageously alter at least a portion of the surface areaof the catalytic objects, which may affect or enhance catalyticbehavior. In one embodiment, a first catalytic object which is initiallycatalytically active may contact a second catalytic object which is notinitially catalytically active, such that the contact causes the secondcatalytic object to become catalytically active. In another embodiment,the contact may enhance the catalytic behavior of a catalyst object. Inone embodiment, the contact may allow the surface of the catalystobjects to become regenerated or “refreshed,” enhancing catalyticbehavior.

With advancing knowledge of the nature of “states of matter”conventional ideas of solid, liquid or, gas may no longer be sufficientto describe the range of states of matter. It may be advantageous toconsider heterogeneous catalyst behavior in the context of knowing thatsuch state differences may be somewhat “fuzzy.” A “surface” typicallydisplays far more complexity than the oversimplified image of a visualplane often used to describe it. Many surfaces may become quite activecatalytically under appropriate conditions. The conventional model of asharp boundary at a surface may be misleading for understandingcatalytic activity. Fundamentally, a surface of a solid may be viewed asa zone or transition region where closely spaced atomic groups insidethe solid taper off as the view looks toward the edge of the surfacezone. Inside, the solid components are closely bound but at the surfacesuch bonding may be disturbed.

The term “surface” in much of the conventional catalyst art has beenapplied in a way that does not reflect a full appreciation of the natureof a surface at its active, small-atomic-scale dimensions. By contrast,certain of the observations of the present invention may be consistentwith a concept of catalyst “surface” wherein, atoms in the interior of acatalyst material, well below the nominal “surface” region—the nearestneighbors somewhat below the “surface”—may also significantly influenceits “surface” properties. Atoms distributed over larger distances thatcover many atom spaces produce long-range processes that also may playan important role. Thus, as described herein, a “surface” is much more azone than a position.

Known quantum mechanical results support the contention that simply byhaving surfaces or materials come very close to each other (a fewmicrons or less), forces may arise and virtual particles may come intobeing. For example, the Casimir effects (Casimir, H. G. B. “On theattraction between two perfectly conducting plates,” Proc. Kon. Ned.Akad. van Weten. 1948, Vol. 51, No. 7, pp. 793-796) may naturally occurin the very small scale of the surface zone of catalysts. Casimireffects, though operating in the tiny surface zone domain of catalysis,have typically not been given attention in the field of catalysts.

In the context of the present invention, without being tied to anyparticular physical phenomena, theory or explanation, it is plausiblethat the inventive catalytic enhancement due to the contacting of solidphase catalytic surfaces may be due, at least in part, to the phenomenonthat as two surfaces approach each other, some quantum uncertainty mayinfluence not only the materials but also the “space” separating the twosurface regions. This may be especially true where the two approachingsurface regions have similar atoms; in such a case, the uncertainty maydictate that some of one “surface” may be found in the other's“surface.” This virtual “tunneling” fuzziness may be only a part of theextraordinarily active zone as two surfaces are brought into proximity.

Brunauer, Emmett and Teller (BET) measurement is a common surfaceproperty test used in describing various materials for catalysts. It isa test of wherein the adsorption of a gas is measured on the surface ofa material. This approach has been based on a theory of Langmuirregarding the processes of gas adsorption at a surface. A controlledamount of an inert gas under pressure is applied under pressure to thetest material. The gas is measured as it is removed by a heatingdesorption process. BET measurement may be expressed as square meters(of equivalent surface) per gram of material under test. Though thetheory of a BET measurement involves many assumptions, the method hasbecome a common specification for catalysts. The conventional thinkingbehind such a measurement was—the more surface area the better.Conventional belief that all catalytic action is surface controlled,suggests more is always better. Recently, however, more studied analysishas shown this to be not necessarily the case (e.g., see U.S. Pat. No.6,831,037).

Material surfaces, even when considered relatively smooth, may berelatively rough on the atomic scale. Examples have been visualized withrecently developed surface scanning techniques showing many surfacepeaks and valleys, terraces, and voids, all present in a typicallyrather uneven way. Another significant aspect of the atomic features ofthe surface zone is the sizable reach of various forces and influences.In the surface zone, things may not be as sharply defined as the scanimages seem to represent. Features often shown atom by atom on a scaleof an atom every few millimeters may not convey the lengthy reach ofinteractions leaping many atoms distance.

Not only is such minute space believed to be significant, also minutetime may play an important role. Things may happen not only over a tinyrange in space of such atom dimensions but in a time of only a fewhundred femtoseconds (10⁻¹⁵ second). Therefore, consideration of theextremely small time intervals in which the short-range catalyticmolecular actions actually occur may be advantageous in developingimproved catalytic processes. Consideration should be given to the verygreat disparity between the femtoseconds actions of chemical bonding andthe much longer time taken by reaction materials to move in and out ofthe surface zone. Thermal molecular velocities are of the order ofhundreds to thousands of meters per second. Thus even a moderate sizedmolecule may only be in the neighborhood of atomic bonding distance of ahundred or so picometers (10⁻¹² meter) for a few hundred femtoseconds.However because of inter-colliding of reactant molecules, the path toand from a surface may be quite indirect and circuitous. Thus thetransport of reaction material may often be the limiting factor ratherthan the time it takes to form a chemical bond. Thus in designingcatalyst materials and systems, it may be important to take into accounthow components of a reaction may get into reaction range and how theymay get away. An important concern then arises concerning how much timeit takes for a catalyzed molecule to leave the environment oncecatalyzed in the surface zone. Catalytic activity may possibly have moreto do with the ensnaring of materials than with overly simplistic ideasfocusing only on the amount of reactive surface area. Catalyzed andreactant materials caught in tortuous interstices that restrain anddelay the entering and leaving of materials may have more to do withproduction rate results than BET measured surface area alone. Even wherea gaseous reactant is involved, BET measurements for much the samereason may not necessarily have a dominant impact on the effectivereaction rate. Consequently, a large surface area built of a denseforest of porosity may also become an inhibitor of material movement.The cohesiveness (sticking together) of like materials may furtherimpair movement. The landscape of a surface may therefore be one of thecontributors to the often very large apparent surface area measured bythe gas adsorption test methods. Though past evaluations of somecatalyst activity seemed to correlate performance with effectiveadsorption area, the correlation was often poor. Large BET values can beobtained through increased pores and surface asperities roughening thelandscape. If carried too far the forest of surface asperities may havea reverse influence on the catalyst production rate by stalling materialtransport. Therefore, in certain embodiments of the present invention,the catalytic materials are non-porous or have a relatively low surfaceporosity.

Heterogeneous solid-phase surface catalysts may in certain instancesre-configure or assemble some molecular species of reactants intodesired products. Such catalyst actions may take place within very shortdistances proximate to some surfaces. Some catalysts act, at least inpart, by breaking apart particular molecular bonds. Others may producenew bond linkages, for example forming polymers from monomer “buildingblock” molecules. The very short time in which such molecular reactionstake place may be an important aspect of all such catalyst behavior. Inthe atomic scale region of surface activity, such events may occur overextremely short periods of time. Such short time behavior appears to notbe appreciated in conventional catalyst research and design. Whether newbonds are created or existing ones are modified by a catalyst, each suchstep may be a discrete transition occurring in extremely shorttime—e.g., in the femtosecond domain. The quantized change of energy insuch an action may increase or decrease the total energy of thecomponents. The quantized nature of such a transition may substantiallylimit the applicability of conventional concepts of mechanical resonantenergy exchange or storage. (Q is a symbol generally used to representthe ratio of resonant energy stored per cycle to energy lost per cycle).Ideas of a “Q” associated with such state transitions may fail becausethe changes are not continuous ones. A discrete transition may be betterrepresented in the form of a state diagram, as shown in FIG. 1, in whichthe vertical direction represents flow of time. Two molecules, one A andone B, (coming from below the wavy line), can interact (the wavy line)through an exchange of a quantum of energy, producing the linkedmolecule A+B and a quantum of energy (or phonon) into or out of thestate as shown at the right of the wavy line. This schematic ispresented, not as a complete theory, but merely a graphic clarifyingevents that may occur in the very brief time of such a reaction. Thatreaction may be either exothermic (energy released) or endothermic(energy absorbed). The time required for the transition (the wavy line)may be extremely short. In fact it may not be possible to say that thetransitioning of entrance states into exit states requires any amount oftime whatever. This is an example of the quantum fuzziness issue. Thevirtue of such a simple diagram lies in representing purely the statedifferences and the feature changes accompanying the event.

Much of the conventional theoretical treatment of surfaces and catalyticactivity by statistically modeling large numbers of elements, whichmotivates much of the conventional approaches to catalyst design andresearch, may fall short by not adequately considering individualinteractions and their brevity. Many known theoretical and empiricalapproaches to catalyst chemistry have dealt in a thermodynamicstatistical way only with overall averages.

Other surface complexities can also play an important role in catalystactivity. Even regular “continuous” metal films that may display nearlyatom-by-atom ordered proximity are rarely smooth on an atomic level.Very pure, nearly perfect semiconductor-crystal materials can approachsuch an almost atomically perfect surface. It is instructive to considerthat even a nearly perfect surface layer may have “defect” properties atits “surface” simply because of the absence of nearest neighbors in thespace above its top layer of atoms. Surfaces may differ from theirinterior or bulk due to discontinuities that may be inherently aproperty of a “surface” (boundary). If such a semiconductor crystalmaterial were “doped” to be of N-type in its interior (electron rich),its surface may still show some P-type properties (hole rich) because ofthe missing electron field on the “empty” side of the boundary. Dopingof a semiconductor material often may be done with just a minutefraction of atoms (for an N-type silicon, about one in 10,000 atoms ofphosphorous). Notably this illustrates some of the extent to whichlong-range properties (many atom-spaced distances) may contribute tobehavior of a surface.

Even atoms within a “solid” array can have a substantial influence onits “surface,” arising from constituent material and organization withininterior and neighboring surface regions. A certain amount of drift ofatoms within such an array may be constantly taking place though theaverage of the array (shape) may appear unchanged. On the very shortdistance and short time scale these movements may have influence onopportunities for various reactions to occur. Temperature of thematerials may also have influence and may work to raise or lower aparticular result as different reactions compete at differing rate, somerising or falling as a result of the balance at a particulartemperature.

It has been observed that freshly “cleaved” surfaces obtained bybreaking a brittle solid in an ultra-high vacuum have high catalyticactivity compared to similar surfaces that are not freshly cleaved. Suchruptured naked surfaces are not yet covered by adsorbed material and canexhibit short-range features known to “hunger” for companions. Such isthe exceptionally active nature of a nascent surface. It is believed, inthe context of the present invention, that surface-to-surface contacteffects may create surface defects creating similar enhanced catalyticactivity as for freshly cleaved surfaces. In context of the presentinvention, the landscape of contacting catalyst surfaces may be changedby each fresh separation following each contact. Again, without beingtied to any particular theory or explanation, it is believed that suchchanges may produce a new crop of surface defects with each separationaccounting, at least in part, to the enhanced catalytic activity andperformance achievable with certain embodiments of the presentinvention. Much conventional research and development in the area ofheterogeneous catalysis intensely pursued large values of measuredsurface gas-adsorption area. This may have encouraged the development ofcounterproductive surface complexity that opposes catalytic productoutput. The typical conventional approaches to catalyst formulationemphasizing particular empirically derived “recipes” of materialsprovide little direction for variation or improvement of the catalyticchemical objective of the catalyst. Consequently, much past developmentwas the result of documenting painstaking experimental work andhistorical operating experience using established catalyst systems ormodest variations thereof. Further improvement in catalyst productivityrequires attention to directly improving catalyst activity and toincreasing transport of material through surface zones. The presentinvention, in certain embodiments, provides materials and methods foraccomplishing such improvements.

This present invention is not limited to any particular catalyst recipeor use for any particular reactant input/product output nor is itspecifically limited in its use to any particular reaction scheme.Examples of catalytic procedures that may be suitable for use in theinvention include, but are not limited to, cracking (e.g., steamcracking, fluid catalytic cracking, hydrocracking, thermal cracking, andthe like), catalytic reforming, acetoxylation, alkylation, ammonolysis,carbonylation, Fischer-Tropsch synthesis, alkane production, pyridineproduction, dehydration (e.g., dehydration of alcohols),dehydrochlorination, dehydrogenation, epoxidation, hydration,hydrochlorination, hydrogenation, hydrogenolysis, isomerization,oxidation, reduction, oxychlorination, petroleum refining, andproduction of synthesis gas and/or products of synthesis gas. Examplesof catalysts and/or catalyst materials that may be utilized in theinvention include, but are not limited to, nickel such as Raney Ni orUrushibara Ni, vanadium(V) oxide, platinum, palladium, rhodium,ruthenium, alumina, silica, platinum rhodium palladium catalysts,Zielger-Natta catalyst, Grubbs' catalyst, Lindlar's catalyst,Wilkinson's catalyst, Crabtree's catalyst, catalyst supported on carbon,alumina, or other materials, derivatives thereof, combinations thereof,and the like. Other catalysts and catalytic procedures that may beemployed in accordance with the present invention are described in Rase,H. F., Handbook of Commercial Catalysts, 1^(st) Ed., CRC Press, 2000,which is incorporated herein by reference.

In fact, the systems, materials, and methods disclosed herein maypotentially be utilized in the context of essentially any solid-phaseheterogeneous catalyst composition for any appropriate catalyticreaction scheme. Such compositions and reactions are extremely wellknown in the art. The disclosed invention may generally apply toessentially any catalyst employing surface-active solid-phase catalystmaterials acting on heterogeneous reactant matter. It is generallyapplicable to the field of heterogeneous catalysis with surface-activesolid-phase catalysts broadly as defined within this disclosure and bythe appended claims.

At least two different types of phenomena may influence the output ratesof a catalyst: First, phenomena acting catalytically upon the desiredchemical bonds in the surface zones; second, phenomena acting to affecttransport of surrounding material, to and from, the surface zones.

Enhanced clearing of trapped surface zone material may be provided bythe surface-contacting action of the present invention, which mayimprove catalytic activity. In certain embodiments, more surfaceclearing may be achieved by adding radiant energy to the active catalystsurface zones to yield even further improvement in catalyst outputresults. This radiant energy can aid the lagging movement of materialsto and from the surface zones.

As discussed above surface contact may be more complex than previouslyappreciated in the field of catalysis. Even slight surface contact mayproduce significant surface changes and defects. Some embodiments, ofthe present invention employ deliberate recurring transient physicalcontact between solid-phase catalyst surfaces to enhance the catalyst'saction upon the target reactant materials.

Certain embodiments of the present invention involve new catalystsurface geometries designed to facilitate and increase the projectedcontact area of surface-to-surface contact events. Catalyst reactorsystems and/or catalytic objects of certain embodiments of the presentinvention are configured to produce frequent surface-to-surface contactbetween catalyst objects, using, in certain embodiments, inventivecatalyst shapes and/or catalyst movement in, for example, catalyticreactors of the invention. In certain embodiments, catalyst objects usedare designed to provide large contact area (e.g., projected contactarea) between a catalytically active surface and another surface, whichalso may be catalytically active, which may be the same or different incomposition, and which may have surfaces that are complementary in shapeand topography facilitating large areas of intimate contact. Such shapesdiffer greatly from those typically used in conventional catalyticprocesses, which are typically spheroids or include similar curved,non-complementary surface shapes. Contact between spheres, especiallyhard spheres, and other similar small radius-of-curvature items,provides only extremely limited contact area. Typical contact betweenhard spheres will typically be very much less than one five-thousandthof the individual object's surface area. Under the conditions typicallyfound in prior art, spherically shaped catalyst objects coming intocontact with one another produce insignificant contact area in contrastto the catalytic object shapes provided according to certain embodimentsof the present invention described in more detail below. In contrast,certain catalyst objects of the present invention, e.g. catalystparticles or pellets, may comprise a plurality of facets (e.g.,essentially planar facets) or mosaic patches on the external surface. Insome embodiments, two such catalytic objects coming into contact witheach other may be shaped to have complementary surfaces such that, for agiven contact event, a projected contact area between the two catalyticobjects is (on average over a large number of contacts) greater than 1%of the catalytically active total external contact surface area of thecatalytic objects. Examples of shapes provided according to the presentinvention include, but are not limited to, a variety of polyhedrons,such as an icosahedron, truncated icosahedron (TICO), cylinder having apolygonal perimetric shape, gear teeth of a gear, and the like. Those ofordinary skill in the art will readily envision a wide variety of othersuitable shapes, each of which is included within the scope of theinvention as defined by the appended claims. The inventive catalyticreaction systems may further include a contact-inducing device which isconfigured and arranged to bring catalytic objects into contact witheach other in the presence of a selected reactant environment to producea desired reaction product. In certain embodiments, the catalyticobject(s) may be contained in a reactor comprising an inlet forintroducing a reactant to the reactor and an outlet through which passesfrom the reactor a product stream. The reactors of the invention maytake many forms that facilitate the creation of repetitive contactbetween catalyst objects therein. For example, convention designs, ormodifications thereof, comprising continuously stirred tank reactors(CSTRs), fluidized bed reactors, slurry bubble column reactors, etc. maybe employed. In addition, in certain embodiments the invention alsoprovides new reactor designs employing, in certain cases, mechanicalapparatuses for creating repeating contact between catalyst objects(e.g., see description of gear pump and roller reactor designs below).In some embodiments, the catalyst object is formed of a catalyticallyactive material. In some embodiments, the catalyst object comprises aninert support material (e.g., a ceramic) coated on at least a portion ofits surface with a catalytically active material.

In certain embodiments, the shape of the catalyst surface provide broadareas of contact, e.g. as with complementary shapes. This providescatalyst object geometries that are very different from typical priorart catalysts and, accordingly, to inventive systems that employ suchcatalysts. With discrete independent catalyst objects, certain inventivecatalytic reactor systems may also cause the objects to move about suchthat the catalyst objects frequently collide in a fashion that they makesubstantial surface contact with one another in the reactant mediumutilized. This can be achieved by placing the catalyst objects incertain environments, such as gaseous, liquid or mixed media, andproviding a contact-inducing device (e.g., a device for agitating theenvironment). Such agitation has been employed in three-phase reactorssuch as slurry bubble column reactors, in continuously stirred tankreactors, and a variety of other configurations. However, conventionalcatalytic reactors that have agitation do not provide the enhancedcontact conditions of the present invention because typical prior artcatalyst object designs do not possess the surface-to-surface contactenhancing properties of certain embodiments of the present invention.

In some embodiments, catalyst objects of the present invention may beused in combination with a contact-inducing device capable of providingagitation or motion to an environment comprising the catalyst objectsand a reactant. For example, the many essentially flat facets of apolyhedron shape, such as the TICO shape described below, may readilyengage in repetitive contact events action when a reactant volumedensely filled with such objects is agitated or stirred in a reactor.These inventive shaped supported catalysts when used in sufficientquantity to provide a high density-of-fill may produce with moderateagitation the desired numerous and frequent recurring contacting betweentheir many faces (which may be essentially flat or of complementarycontour). Continuously stirred tank reactors (CSTRs) known in the artcan be an appropriate apparatus for such a process use. In addition toCSTRs, widely employed Slurry Bubble Column Reactor systems that utilizebubbling gas to agitate for example a Fischer-Tropsch type ofhydrocarbon synthesis reaction may also be used in conjunction withcatalysts of the present invention, such as a TICO type catalyst. Incertain embodiments, especially those employing a large number ofagitated catalyst objects in the form of particle-like objects, it maybe desirable to avoid a three-dimensionally shaped catalyst object thatis symmetric in a manner that permits aggregation (e.g., “lock-up”) whenmany catalyst objects are close packed. For example, this may occur withcubic block-shaped objects upon agitation. In certain embodiments,catalyst object forms are provided that allow the desired frequentsurface-to-surface contact event but minimize tendency to aggregate in alocking fashion. Inventive asymmetries are exemplified in the severalexamples given below; however, there are many other geometricpossibilities meeting this need that will occur to those skilled in theart.

In certain embodiments, a mechanical actuator, mechanism or apparatus towhich at least one catalytic object is attached or mechanicallyinterconnected may be employed to place at least two catalyst objects(or one catalyst object and a non-catalytic object) into contact, suchthat a projected contact area between the two objects is greater onaverage than about 1% of the catalytically active total external contactsurface area of the catalytic object(s). For example, systems in whichmeshing gear teeth, which include a surface comprising a catalyticallyactive material, contact a reactant may be used (e.g. see FIG. 7). Thereare many presently known forms of gear pumps that may serve suchfunction by positioning the catalytically active gear teeth in aninterdigitated fashion and rotating the gears, creating contact betweensurfaces of the gear teeth. Additionally, an inlet and outlet may beincluded in the catalyst reactor system such that reactant material maybe circulated over the catalyst objects, for example at least in partdue to convection created by the moving gears.

Other embodiments of the present invention may additionally employcylindrical reaction chambers or pipes comprising an interior surfacewhich may be made catalytically active. When brought into contact withother object(s), such as other catalytic object(s) of a similarcomposition, in a suitable reactant environment, contact events of theother contacting object(s) with the catalytically active interiorexternal surface of the reaction chamber may produce the desired contactconditions to promote enhanced catalytic behavior. Systems of this kindmay be readily applied to circulate fluids, gases and such thuscombining desired fluid moving functions with intended catalyticprocesses.

A exemplary configuration for utilizing shaped contacting catalyticsurfaces employing gear teeth having catalytically active surfaces onthe teeth id shown in FIG. 7. Such gears naturally operate producingrapid transient effective surface-to-surface contact on each engagingtooth surface. Gear pump devices are known having specially shapedcontacting teeth suitable for fluid pumping. Many forms of commercialgear pumps exist. Such a mechanism combines surface contacting functionswith fluid pumping functions often useful for many catalyst processes.Such catalytic gear pump-like systems have uniquely effective usesconsidering their natural high-pressure capability along with large flowrate capabilities under even extreme temperature conditions. By having adesired catalytically active surface material on the engaging gear pumpteeth, the conditions for the subject system can be achieved in avariety of otherwise difficult conditions. Well established processesmay be used for depositing catalytic materials on such gear toothsurfaces.

Another configuration of this type employs multiple individual gearpumps. These may be used inside a reactor to produce mixing andagitation of the reactant materials within it. Such devices oftenutilize the action of two or more gears rotating together so that fluidis swept into the merging teeth and exits on the parting teeth side ofsuch an arrangement. There are many forms of this kind of device knownin the art. Some employ multiple gears, some planetary systems. Teeth ofvaried forms can be used in such systems.

It may be desirable for the engagement of such teeth to develop thelargest contact area and travel over each tooth face that is coated withthe appropriate catalyst material. The pressure between the teeth mayalso be maintained by an appropriate force generating motor or othermechanism for exerting just enough force to insure significant engagingcontact over the fullest extent of tooth surface possible.

Another configuration for such a gear pump system may be a serialarrangement of fluid travel from one gear pump to a next one seriatim tocreate an extensive surface coverage by a circulated fluid reactant.

Another property which may be convenient for catalyst processes is theability of such pumps to operate in very high-pressure conditions. Thistype of pump can either generate such pressures or operate the engaginggears without any housing containment simply inside a controlledreactant chamber environment. The gear engaging system may be configuredand operated to develop sufficient total surface-active contact areaand, to run high enough gear speeds to optimize contacting action so asto obtain the desired output of reacted product. The tooth shape may beany one of the well-known types designed for angled or helical or othergeometries that increase the available contact area on each toothengagement.

The patent literature shows many examples of pump designs potentiallyadaptable to the applications described. For example, two such pumpstructures are described in U.S. patents are: U.S. Pat. No. 5,660,531and U.S. Pat. No. 6,518,684.

Another embodiment of the present invention may involve a catalyticreactor system comprising catalyst objects configured in the shape of aroller bearing arranged to create the multiple contacting and separatingaction modality of certain aspects of the present invention (see FIG.11). The roller bearing surfaces may be coated with a catalyticallyactive material. Structures of this type can be immersed within areactant medium within a reactor or in a flow stream of such a reactor.This type of embodiment with appropriately designed materials may alsofacilitate use with a very wide range of temperature and/or pressure.

FIG. 11 illustrates an embodiment of an inventive catalytic reactorsystem 70 that need not employ catalyst pellets or particles but ratheruses the containment vessel, with an inner surface 72, and a mechanismthat also provides agitation and stirring action of catalytic objects.Cylindrical reactor 70 includes a series of spring loaded rollers 74,which are coated with a catalytically active material, arranged on acarrier 76 which is rotated about a central shaft 78. Reactor 70 mayfurther comprise inlets and outlets, not pictured, to allow for thecirculation of reactant material within the reactor vessel. The rollers74 and/or the internal surface 72 of the reactor containment vessel thatthey contact and press on may be coated with a desired catalyticallyactive surface material. Carrier 76 rotates the rollers 74 to makeinterrupted contacting events on particular areas of the catalyticsurfaces of rollers 74 and/or surface 72. The rotation also provides away of agitating and stirring the contents (e.g., reactant material).Such a vessel can be either batch or continuous flow operated. Theparticular geometry illustrated is but one case of many possibleconfigurations as would be appreciated by those skilled in the art. Thisinventive structure can be constructed in essentially any size deemedappropriate for the objectives selected. Cylindrical containment vesselsalso advantageously lend themselves to extremes of operating pressureand temperature. Magnetic coupling can be used to generate rotation ofcarrier 76 in a sealed systems.

In another embodiment, gear pump systems like those discussed above canoptionally be combined with a system as illustrated in FIG. 11 forpressure and flow advantages. The flexibility of the inventive catalyticreactor systems illustrate the many possibilities for performing severaldifferent kinds of these reactions on a feedstock stream by couplingvaried reactor configurations. This can be done serially or as abranching network thus lending itself to many flexible integratedindustrial process configurations within the scope of the invention.

Certain embodiments of the invention comprise the use of ananvil/striker catalytic reactor apparatus, which in certain embodimentsmay be sized and configured to be particularly well suited forsmaller-scale analytical testing, experimentation, process/materialsoptimization, and comparative testing applications. Two such embodimentsare shown in FIGS. 12 and 13, respectively, which, as explained in moredetail below and as shown in the Examples 6-15, may be especially usefulas a pilot-scale testing and analysis devices.

FIG. 12A provides a cross-sectional view of an exemplary embodiment ofan anvil/striker catalytic reactor apparatus 80. FIG. 12B shows atop-view illustration of the striker apparatus, while FIG. 12C shows atop-view illustration of the anvil apparatus. As shown in FIG. 12B, astriker contact 84 is positioned on a bottom side of striker leaf 98,and an eddy-current sail 92 is positioned on a top side of striker leaf98. Striker leaf 98 is held in an elevated position by striker base 94.As shown in FIG. 12C, anvil apparatus 80 includes an anvil base 90 andan anvil carrier plate 88 positioned on a portion of the anvil base 90such that the anvil carrier plate 88 has a top surface essentially flushwith the surface of the anvil base 90. The anvil carrier plate may bealigned with pins 89. An anvil contact 86 is positioned on a portion ofthe anvil carrier plate 88. In the anvil/striker apparatus 80, strikerapparatus 98 is positioned on top of the anvil apparatus such that anvilbase 94 contacts a portion of anvil base 90. Also, striker leaf 98 ispositioned above the anvil apparatus such that striker contact 84 ispositioned directly above anvil contact 86.

The anvil contact 86 and striker contact 84 may be soldered to the anvilcarrier plate 89 and the striker leaf 98, respectively. The solder maypreferably be a high temperature gold/silicon type such as those used insemiconductor structures. A thin foil (<0.002″) of such solder may fuseeach of these metal parts in a reducing atmosphere furnace. One or bothof anvil contact 86 and striker contact 84 may comprise a catalyticmaterial. This type of assembly preserves the flatness and parallel formof the parts. The design allows repeated tests with different catalyststo maintain identical operating behavior.

In this configuration, striker contact 84 is capable of contacting anvilcontact 86 by movement of striker leaf 98. Screw 96 may be used tocontrol the force with which striker contact 84 contacts anvil contact86. In the illustrative embodiment, the anvil contact 86 has a largersurface area than the striker contact 84. For example, the anvil contactmay have a surface dimension of 5 mm×5 mm, while the striker contact mayhave a surface dimension of 2 mm×2 mm.

The anvil contact 86 and/or striker contact 84 may be coated with acatalytically active material, as described above. The striker contact84 may be brought into contact with the anvil contact 86 such that acatalyzed product is formed on the area of contact (e.g., the surfacearea of the striker contact and the “struck” portion of the anvilcontact).

The excess or “un-struck” area of the anvil contact (for example, a 1.5mm wide frame having 21 mm² of anvil surface) is exposed to the sameenvironment, however will show substantially less catalyzed product onits surface than on the 2×2 “struck” area (4 mm²).

Various catalyst materials, reactant materials, operating temperaturesand pressures, etc., can be tested with the present system.

Referring to FIG. 13, a second exemplary embodiment of an anvil/strikercatalytic reactor apparatus 100 containing an anvil/striker assemblywithin an enclosure 140 is illustrated. An embodiment of this apparatusis described in much greater detail below in Example 6 and is describedhere only briefly. Striker assembly 120 is positioned relative to anvilassembly 110 such that the striker can come into controllable andrepeated contact with the anvil. The striker assembly 120 may beconnected to an electromagnetic drive system, e.g. inductive coil drivenlinear actuator 130, which can measure and control the positioning andmovement of the striker and the applied force during contact events. Inthe illustrated embodiment, a gas bearing 132 used provide a very lowfriction passage through enclosure 140 of push rod 131, which drives thestriker 300 (FIG. 15) A set of inlets 142 can introduce reactantmaterial, such as reactant gas, into apparatus 100, and a set of outlets144 can be used to evacuate the reactant gas from apparatus 100. Incertain embodiments, each of the three illustrated reactant inlets 142and product outlets 144 can be in fluid communication with differentportions of the catalytically active surface area of the anvil 200 (FIG.14) of the anvil assembly 110 (e.g. struck and unstruck portions of theanvil in the illustrated example).

The techniques of present invention are not believed to be limited intheir utility to particular catalyst materials or catalyzed reactionsand may be applied to a wide range of surface-active catalysts andreactions able to be catalyzed by these catalysts. Essentially theentire known catalog of surface-active catalysts may potentially bebenefit by application of the surface-to-surface contacting systems andconfigurations of certain embodiments of the present invention. Catalystmaterials other than metals, such as oxides or ceramics, may be able tobenefit from effective contact events within the context of the presentinvention. Those of ordinary skill in the arts of heterogeneouscatalysis, using no more than the knowledge and resources available tothose skilled in this art, given the teaching and guidance provided inthe context of the present invention, will be able, without undueexperimentation and burden, to select appropriate catalytic materialsfor a particular desired reaction and to fabricate such catalyticmaterials into the catalyst objects and catalytic reactor systems of thepresent invention. Those of ordinary skill in the art will be able toperform screening rests and routine testing and optimization, e.g. suchtests may performed in a similar fashion as the procedures describedbelow in the Examples 6-15, to select appropriate or optimal conditionsfor implementing the inventive techniques involving creating and/orenhancing surface contact of catalytic objects and to confirm that theinventive techniques yield increased catalytic activity in their chosensystem.

In some embodiments, catalyst reactor systems of the present inventionmay comprise a catalytically active material that forms a catalyticobject or that is present on at least a portion of the surface of thecatalyst object. Catalytically active materials are known in the art,and can be chosen to suit a particular application. In certainembodiments, combinations of metals such as alloys or other metallicmixtures can provide advantages for specific catalytic activity. Forexample, combinations, in which the different components have differentvalence or oxidation properties may produce more active sites forcatalysis upon contact with like surfaces. In selecting metal atoms forsuch combinations, elements from adjacent periodic table columns may bechosen. For example, a transition metal from a certain column on theperiodic table may be alloyed with a transition metal from an adjacentcolumn, such as a preceding column or a following column. Examples ofsuch combinations may include elements from at least two of columns 9,10, and 11 of the periodic table. For example, a transition metal fromgroup 10 (e.g., nickel, palladium, platinum) may be alloyed with a smallamount (e.g., 0.05 wt %, 0.10 wt %, 0.25 wt %, 0.50 wt %. 0.75 wt %, 1.0wt %, 5.0 wt %, 10 wt %) of a transition metal from adjacent column 9(e.g, cobalt, rhodium, iridium, etc.) In a specific embodiment,palladium metal may be alloyed with 0.25 wt % iridium.

Inventive systems employing the enhanced catalyst contacting techniquesand configurations described above may be useful in ameliorating theoften problematic, “regeneration” and refreshing operations common withindustrial catalytic operations. Surface-to-surface contact may act, atleast in part, as a form of continuous regeneration or re-activation. Inaddition to significant improvement in catalytic action the presentinvention may, in certain embodiments, enable increased selectivity forresultant products by permitting a greater range of operating parametersto be utilized. The present invention may make possible utilization ofconditions not previously effective or practical in conventionalsystems.

Many configurations are possible within the context of the presentinvention. Presented below are examples which should be considerednon-limiting cases of a very large scope of possible applications andconfigurations within the scope of the present invention. Others willoccur to those skilled in the arts; therefore only the appended claimsshould define the limits of the inventive subject matter.

In another embodiment, the catalyst reactor system may be operated atsupercritical conditions (of temperature and pressure) to obtain adesired molecular species for catalytic reaction. This can be done in amore or less continuous fashion or because of the severity of suchthermodynamically active conditions it may be done transiently in arepetitive manner to lessen the burden of such extreme conditions onmaterials and equipment.

Other embodiments of the present invention may improve the transport andrelease of catalyzed material and reactant to, from, and/or in thesurface zone. Though the system's contacting action itself may alsofacilitate significant benefit in material transport, such effect may befurther enhanced in certain embodiments by application of radiantenergy. The exciting action of radiant energy incident on the catalyst(for example, sonic, ultra-sonic, photonic, particle and/orelectromagnetic energy) may improve the movement of material to, from,and/or through the surface zone. As indicated above, the entrainment ofmaterials in the surface zone from micro cavities or cohesion can be aretarding process with a time factor many times that required by theactual catalytic transformation.

Catalyst objects of the present invention may, in certain embodiments,be configured as particles or pellets that have geometries includingmultiple projected contact areas and/or facets/mosaic patches, eachhaving an external surface area typically 1%, 2%, 3%, 4%, 5%, 6%, 7%,8%, 9%, 10% or more of the total active external surface area of anindividual catalyst object. The principle of the subject system may berealized in a wide variety of sizes, shapes and configurations, whichmay be chosen for a particular application, that provide significantprojected contact area greater than 1% of the total external activesurface area of an individual catalyst object. One illustrative shape isthe cylindrically symmetric catalyst object with nine longitudinal flatfacets along its long axis surface shown in FIGS. 8 and 10. Other shapeswill suggest themselves to those skilled in the arts when consideringthe possibilities for application of the principles of the subjectinvention. Differing desired conditions of use and economic factors alsoaffect such choices.

The catalyst objects may be a solid catalyst material, a layeredconstruction, a hollowed structure, or the like. For example, nickelmetal often used in catalysts might be used in a solid form, its shapeconforming in principle to the multifaceted construction of certainembodiments of the present invention. Many configurations for suchaction are conceivable within the scope of the present invention.

For certain applications of the present invention small specially shapedcatalyst objects may be desirable. Supported catalyst objects may beutilized for reasons of freedom in shaping the objects and for economyof manufacture. For example, ceramic materials may be utilized forsupported catalyst substrates. Stability, high temperature endurance andchemically inert qualities may make ceramics suitable for a wide rangeof process conditions. As discussed previously the present inventionprovides inventive catalyst geometries. In order to form suchgeometries, effective methods for molding shapes more complex andprecise than can readily be achieved with extrusion methods common forfabrication of ceramic materials may be advantageously employed. Use ofsuch a molding process may be advantageous for achieving the degree ofshape asymmetries discussed above as being useful to avoid lockingbehavior of catalyst objects whose shapes interlock too easily whendensely filling the reaction space.

In certain embodiments, materials that can be produced in powdered formcan be mixed with thermally moldable plastics and formed into a desiredshape using known powder injection molding (PIM) techniques. Thesemethods have been developed to allow the very productive and economicaltechnologies of plastic molding to be realized for the fabrication ofmetal and ceramic parts. When ceramic powders are used, such methods aresometimes called ceramic injection molding (CIM). Among suchtechnologies CIM processes employing alumina ceramic may be particularlyuseful for forming catalyst substrates. Such methods may be utilized forthe fabrication of many catalyst objects within the scope of the presentinvention. Materials for performing such methods are available from BASFAG of Ludwigshafen, Germany, who also publish guides and handbooksdescribing fabrication methods (see Piotter, et al., Sadhana, Vol. 28,Parts 1 & 2, February/April 2003, 299-306).

Some references describing conventional catalyst processes employingsupported conventional ceramic catalyst carriers have reportedsignificant wear from abrasion caused by agitation. Conventionally,concerns have been directed to minimizing effects of mechanical wear ofthe ceramic substrates they employed. The approach generally taken wasthrough manipulation of the composition and processing of the ceramic.The generally recognized phenomenon of such wear has been dubbed“attrition” of the catalyst. Wear particle detritus common from suchbehavior have been given a special name—“fines.” Such fines particlesnot only clog filters and interfere with process machinery but that wearmay also result in reduced catalytic activity. Current ceramictechnology has employed additives to a pure aluminum oxide ceramic veryoften used for catalyst support substrate material. Titania (titaniumoxide powder) with other material added to it (for example barium in alesser proportion) has been blended in to improve resistance toattrition. Durable fully sintered pure alumina molded parts produced bythe CIM process described may be adequate for many uses but wear factorsshould be considered for each specific process in selecting substrateshape, materials and processing conditions. To improve abrasionresistance an alumina material (e.g., AO-F alumina available from BASF)may be blended with one to five percent titania powder with the optionaladdition of one percent or less of barium to neutralize any sulfatecontent affecting abrasion performance.

The function and advantage of these and other embodiments of the presentinvention may be more fully understood from the examples below. Thefollowing examples, while illustrative of certain embodiments of theinvention, do not exemplify the full scope of the invention.

EXAMPLES Prophetic Example 1 Manufacture of a Catalyst Object

Catalyst objects are made using moldable alumina powder material soldunder the trade name Catamold® type AO-F available from BASF AG ofLudwigshafen, Germany and their distributors in other countries. TheAO-F material is made of a 99.8% purity aluminum oxide that iscompounded as a finely divided powder blended with about 20% polyacetalplastic material. This enables it to be handled and molded like aplastic using existing screw plasticizing molding equipment. Evencomplex shapes are possible with such techniques. The full process asdescribed below exists as a commercial operation used routinely toproduce ceramic molded parts. The parts as first molded by such aprocess actually are not yet fully ceramic, requiring two processingsteps beyond the plastic molding step to become hardened durable ceramicshapes. Because of the amount of plastic material added to make possiblethe plastic molding process, as-molded parts are designed to be forexample 20 percent larger than desired for the finished part. Theparticular polyacetal plastic chosen for the added material enables suchmolded parts (“green” parts) to be chemically treated to eliminate allthe added plastic. This is done in a process the first step of whichgradually raises the room temperature parts (at a rate of 3° C. perminute) until stable at 270° C. In that heated environment the greenparts are then exposed to nitric acid vapor for about one hour. Thisprocess, called “debinding,” rapidly converts to a gas all the plasticin the molded part. Thus debound, devoid of the polyacetal, somewhatporous but firmly and precisely shaped, the now “brown” parts are in thesecond step directly carried into a sintering operation. The temperatureis gradually increased at 3° C. per minute during the next 7½-hourperiod arriving at the full sintering temperature of 1610° C. Afterremaining there for about an hour the parts are slightly more rapidlycooled at 2° C. per minute to 400° C. then further slowly cooled at 3°C. per minute to 50° C. or room temperature. The now fully hardenedsolid shaped parts can be handled, ready for any further steps.

This sintering cycle accomplishes several purposes: 1) it preciselyshrinks the parts to the designed size; 2) it fuses the part into anon-porous precisely shaped solid ceramic such that; 3) the resultingsurfaces then become hard and glassy-smooth. For beneficial control andeconomy, the entire debinding and sintering operation cycle can be donein one continuous automated “pusher” type tunnel furnace system. Thesurfaces of parts so sintered emerge from processing well-suited forcoating with any of a variety of catalytically active materials desired,for example, palladium or platinum metals or combinations as describedabove. The foregoing methods can be utilized as the fabricationtechnique for the supported catalyst object examples given below.Economic advantage and shape possibilities using this CIM molding andsintering process make it potentially valuable for application forforming the catalytic objects of the present invention.

Prophetic Example 2 Manufacture of a Supported Catalyst Shape

This example illustrates manufacture of one selected shape for amoderate sized supported catalyst object about 3 mm in diameter that hasmultiple advantages over a sphere.

The shape of the catalyst object is essentially a truncated icosahedron10, as shown in FIG. 3, a variant of a soccer ball shape, havingthirty-two essentially flat planar faces, twenty of which are hexagonalfaces 12 and twelve of which are pentagonal faces 14. (The Euclidianideal geometric form of truncated icosahedron 10 is shown in FIG. 2.)The catalyst object has general spherical symmetry yet providesrelatively increased projected contact area when compared to a sphere,as each of the thirty-two projected contact areas may be greater insurface area than a few percent of the object's total external surfacearea. The total surface area of this particular polyhedral shape is overforty eight percent larger than a sphere of the same nominal diameter.

FIG. 4A shows another view of a truncated icosahedron, while FIG. 4Bshows a view of all thirty-two faces of the truncated icosahedron laidflat and adjoining showing the relationship of the faces.

To synthesize a catalyst in the shape of a truncated icosahedron, aceramic supported catalyst substrate having the desired shape is formedby the CIM methods described in Example 1 above. The ceramic substrateis then coated with selected catalyst material. For reasons ofdurability and ease of fabrication the shape is modified in several waysfrom its ideal soccer ball shape. This modified shape hereafter iscalled a TICO. First, the sixty edges of the facets are rounded or“softened.” As shown in FIG. 5, facets 22 and 24 meet at edge 20, whichis slightly rounded to eliminate the sharp edge giving rounded smoothfacet-edges having a radius of curvature 26 of about 0.08 mm.

Also, in embodiments where the catalyst object is synthesized using amold, the facet angle at the part-line of a mold may be less than 90° toaid in release of the catalyst object from the mold. FIG. 6 shows acatalyst object 30 having a facet 38 adjacent to a mid-planeparting-line 36 of a mold 32. Line 34 illustrates a 90° angle at moldpart-line 36. The facet 38 may preferably be slightly tilted so theseadjoining faces make an angle slightly less than 90°, with respect tothe plane of the parting-line. (The parting line is the open face of themold for such parts.) This facilitates the molded parts being moreeasily released from the mold cavity thus avoiding a part too large toleave the mold cavity. The half cavity mold opening for such parts canbe slightly larger than the part to enable it to release easily from themold.

In the present example, catalyst particles are fabricated such that eachsuch truncated icosahedron has thirty-two essentially planar facets.These facets increase available projected contact area—a strategy instark contrast to minimizing projected contact area, as in a sphere. Thesubstantial difference in projected contact area complements therelative increase in possible contact events possible with an agitatedmultitude of such faceted TICO-shaped catalyst objects packed within areactor.

The resulting numerous frequent contact conditions are observed toproduce a relatively increased amount of catalysis for a selectedreactant. TICO-shaped supported catalyst carriers of the present exampleare molded using the process described above in Example 1 and coatedaccording to needs. Many methods exist that are familiar to thoseskilled in the arts for deposition of materials on substrates that canbe used to deposit desired metals, oxides or other catalytic materialson TICO surfaces. The techniques can be selected from varied processesranging from liquid deposition to vacuum evaporation. In the presentexample; cobalt metal-coated TICO is used in a Fischer-Tropsch reactionwith appropriate synthesis gases in either slurry bubble column reactor(SBCR) or a continuously stirred tank reactor (CSTR). Thermal toughnessof the TICO construction of the present example lends itself to such ahighly exothermic process.

Prophetic Example 3 Manufacture of a Nine Sided Cylindrical CatalystPellet

FIG. 8 illustrates another inventive form of a catalytic object andsystem comprising a catalyst pellet that employs a nine-sidedcylindrical shape 40. FIG. 8A illustrates a side view along the lengthof the cylindrical pellet, while FIG. 8B illustrates a transversecross-sectional view. The methods described above in Example 1 for CIMmolding are used to make this inventive shape. The unusual number andasymmetric arrangement of the essentially planar facets 48 lends itselfto good mixing and surface-to-surface contact with minimal lockingeffects.

In FIG. 8, an illustrative embodiment of the cylindrical pellet isshown. Cylindrical pellet 40 has an overall length 42, with theessentially planar facets having a length 44. A domed end of the pellethas a length 46. The nominal diameter of cylindrical pellet 40 is shownby 52. In this particular example embodiment, the cylindrical pellet is11.5 mm long, with nine, essentially planar facets each having a lengthof 7.5 mm. The length of the dome end is 1.95 mm. The diameter 52 of thecylindrical pellet is 5.65 mm. Edges 50 are rounded as described abovein Example 2.

The size illustrated is arbitrary as the concept is broadly applicableto wide range of possible sizes and alternative numbers of facets. Theuse of other solid materials will also occur to those skilled in thearts. The size of the present example in FIG. 8 has about three timesthe contacting area of the illustrated and previously described TICOshape having a 3 mm diameter. The larger contact area of a facet ofcylinder 40 can be essentially flat and smooth to be fully effective incontact events. The maximum projected contact area of this shape is morethan 8 percent of the total external surface area of the particle. Thisfactor for the above-described TICO shape may be typically from justover 2 percent for the smaller facet to just over 3 percent for thelarger facet. The FIG. 8 shape may be readily molded using thepreviously described CIM process or many other possible known moldingtechniques. The domed ends, as shown in FIG. 10, may minimize attritionof such parts in use such as could occur from simple squared-off endgeometry. FIG. 10A illustrates a cross-sectional view along side of thelength of the cylindrical pellet, while FIG. 10B illustrates a side viewdown the length of the cylindrical pellet. The dome design allows for asmooth transition from the domed end to the body of the cylindricalpellet, which comprises essentially planar facets. The diameter 60 isthe maximum diameter of the body of the cylindrical pellet, while thediameter 62 of hemispherical dome is relatively smaller, allowing for asmooth transition from the body to the domed end.

Prophetic Example 4 Manufacture of a Hecatohedron Catalyst Pellet

The hecatohedron shape of the catalytic object illustrated in FIG. 9comprises a relatively diametrical symmetry that requires lessmodification to make the molded object more easily release from a moldcavity. The external surface area of each facet is smaller than the TICOobject for a given nominal diameter because the shape approaches moreclosely that of a sphere. Nonetheless the large number of essentiallyflat facet surfaces yields projected contact areas considerably largerthan with for a spheres of the same diameter. The smaller facets enablethe shape to be relatively easily fabricated with a desirable level offlatness and fine surface finish. This “HECA” catalyst shape is readilymoldable with the CIM process discussed above. The irregular facetshapes can moderate the locking tendencies of spherical symmetry.

Example 5 Catalytic Enhancement by Surface-to-Surface Contact

In order to observe the contacting effect on the catalytic activity ofpalladium metal, and alloys thereof, an experimental catalyticanvil-striker contacting apparatus similar to that illustrated in FIG.12 and described previously was fabricated in the following manner:

Two reed elements were obtained from a reed relay capsule ofapproximately ¼ inch diameter. A portion of the surface of each reedelement was abraded away, and small samples of palladium metal weresoldered to the stripped down reed pieces. A 3 mm×3 mm (approximately)palladium sample was soldered to one reed, while a 4 mm×4 mm(approximately) palladium was soldered to the other reed. An externalmagnetic field was applied to control movement of the reed pieces, so asto bring the palladium samples into contact with each other. Thus, themodified reed elements functioned to provide a simple contact openingmeans. The modified reeds were set up to be normally closed with acontact force of 6 grams as read by a 0 to 15 grams dial type springdynamometer used to set relay spring force. The reed pieces were mountedto microscope glass slide as a base using litharge cement. The upperreed was contacted by the lower reed and bent until 6 grams force justopened the contact as determined by an ohmmeter.

The slide assembly was placed in a 1 inch inside diameter Pyrex glasstube for exposure to the reactants (methane gas). The volume of theinterior of the tube was approximately 75 ml. The ends of the tube wereclosed with a single-hole silicone rubber stopper on each end. Methanegas was flowed through the Pyrex tube at a rate of 5 to 10 ml perminute. An external wire coil surrounding the tube was driven by a poweramplifier from a function generator to provide the magnetic openingforce for the assembly. The palladium contacts on the reeds were broughtinto contact at a rate of about five times per second, over a timeperiod between several hours to as much as one day. Significant organicdeposits were found on the contacts. The longer period showed moredeposits. Gas chromatography showed that the molecular weight of thedeposits was more than 20,000 in polystyrene equivalent. The palladiumused was varied between pure palladium, a palladium-ruthenium alloycomprising 10% ruthenium, and a palladium-silver alloy comprising 10%silver. The deposits appeared thick and tacky.

Working Examples 6-14 Striker/Anvil Catalytic Reactor Test (SAT)Apparatus and its Use to Observe Enhancement of Catalyzed Reactions byCatalyst Object Contact

The SAT Apparatus

An SAT apparatus as pictured in FIG. 13 and described above was designedto permit evaluation of contact effect with a variety of solid catalystmaterials operating in a structure that provides a closed space reactionvolume through which carrier and reactant gases may be flowed.

The SAT apparatus incorporates an electronic digitally controlledelectromagnetic driven mechanical system to produce repeated precisecontact force between two pieces of catalyst materials (e.g., strikerand anvil) in a precisely parallel meeting manner.

A large (30″×60″) heavy duty welded steel cart with 8-inch pneumatictires (not pictured) was used to support the total weight of the SATapparatus (i.e., more than 700 pounds), as well as a battery back-uppower supply (not illustrated), a line-regulator-conditioner (notillustrated), gas flow piping and controls (see, e.g. FIG. 16), adigital-computer controlled electronic digital drive control system (notillustrated), and a computer with 20″ LCD monitor (not illustrated). Thecart also supports gas flow valves, piping and flow monitoringRotameters (see FIG. 16). An Agilent Mass Sensitive Detector (Model5879) 502 is positioned adjacent to the cart and connected to the SATsystem 100 via a selector valve 504 and piping within a heated enclosure(not illustrated) attached to the cart. Gas cylinders (not illustrated)supplying the feed gases are connected to the gas control panel 507 onthe cart through piping from a cylinder storage area close to the cart

The catalyst materials are provided in the SAT apparatus via a removablestriker post and a removable anvil carrier insert, such that thecatalyst materials may be easily changed. Small pieces of catalystmaterial are brazed to the replaceable striker post and anvil insert sothat the manner in which the two catalyst materials contact one anotheris constant over various samples. The anvil and striker catalystmaterials are ½ mm thick of mill rolled stock fabricated to be flat andparallel to within 30 micro-inches and formed as strips either 3 mm wideor 5 mm wide. The strips have a smooth bright surface finish typicallybetter than 0.5-micron roughness. The 3×3 mm striker and 5×12 mm anvilwere cut from the strips with a fine 8/0 jewelers saw and the cut edgesfiled to remove any “flash.”

FIGS. 14A-G show various views of anvil assembly 110 of SAT 100. Anvil200, which is brazed to anvil insert 201 (FIG. 14B), is positionedbetween inlet port 230 and outlet port 220 such that, when reactant gasis fed from inlet port 230 to outlet port 220, the reactant gas flowsacross the width of anvil 200 and contacts anvil 200. FIG. 14D show aclose-up view of inlet port 230 and outlet port 220. Inlet port 230comprises inlets 232, 234, and 236, through which reactant material maybe introduced. Inlet port 230 further comprise nozzles 276, 278 and 280,which introduce the reactant material to the surface of anvil 200.Nozzles 276, 278 and 280 are arranged such that the nozzle openings arepositioned just above the surface of anvil 200 and about ½ mm from theedge of anvil 200. Nozzles 276, 278 and 280 are angled downward about 3degrees from parallel with the plane of the anvil surface to ensure thatthe reactant gas contacts anvil 200. Nozzles 276, 278 and 280 are shaped(e.g., substantially rectangularly shaped) such that, when the reactantgas is introduced to anvil 200, the reactant gas has laminar flow. Thebottom edges of nozzles 276, 278 and 280 are precisely located ¼ mmabove the top surface of the anvil insert 201. Similarly, outlet port220 comprises complementary nozzles 270, 272 and 274, through which thereactant/product gas can exit after contacting anvil 200. Nozzles 270,272 and 274 are also arranged such that the nozzle openings arepositioned just above the surface of anvil 200 and about ½ mm from theedge of anvil 200, and the bottom edges of nozzles 270, 272 and 274 areprecisely located ¼ mm above the top surface of the anvil insert 201.Outlets 222, 224 and 226 are connected to gas outlets 144 (see FIG. 13)to evacuate the reactant/product gas from the SAT apparatus 100 and tofeed the streams to the Mass Spectrometer analysis system (Agilent 5879MSD). Resistor 202 (e.g., a 1000 mW resistor) eliminates static charge.Ceramic components 290 and 294 insulate the anvil 200 from current, anddowels 292 and 293 guide the positioning of anvil 200 (FIG. 14G).

A particularly advantageous feature of the SAT apparatus allows variousportions of anvil 200 to be studied simultaneously. FIG. 14E shows a topview of a portion of anvil assembly 110, wherein dividers or “fences”240 and 242 are positioned across the width of and in contact with anvil200 to define portions 210, 212 and 214 of anvil 200, and to preventcrossover of reactant/product gas from one portion to another portionduring operation. Dividers 240 and 242 may be held in place, forexample, by slots or grooves in inlet port 230 and outlet port 220. Insome cases, the dividers 240 and 242 may be made of glass, or any othermaterial which may physically isolate portions 210, 212 and 214 from oneanother. In the present example embodiment, thin Borosilicate (6milthick) glass “fences” that are 5.5 mm high and 18.3 mm long were used.Reactant gas was introduced in a direction 250 via inlets 232, 234 and236, such that reactant gas exiting outlet 276 only contacts portion 210of anvil 200, reactant gas exiting outlet 278 only contacts portion 212of anvil 200, and reactant gas exiting outlet 280 contacts only portion214 of anvil 200. This arrangement may be advantageous in that thedifferent portions of anvil 200 may be comparatively evaluated under thesame reactant conditions to determine the relative enhancement incatalytic activity portion 212 when contacted by a second catalyticmaterial.

In some cases, the dividers 240 and 242 are not necessary, as thelaminar flow of reactant gas can be controlled, for example, bycontrolling inlet and outlet flow rates, such that there issubstantially no crossover of reactant gas from one portion to another.

In this example, reactant gas flowed in a direction 250 from inlet port230 to outlet port 220. It should be understood that, in otherembodiments, reactant gas may flow in a direction opposite to direction250 (e.g., from port 220 to port 230).

Anvil 200 was configured to have a larger surface area (5×12 mm) thanthe second catalytic surface (i.e. the catalytic surface of striker 300(3×3 mm) and was arranged such that the striker contacted only portion212 of the anvil 200 during operation. In other words, portion 212 ofanvil 200 was contacted by a second catalytic surface (i.e., the striker300) in the presence of reactant gas, while portions 210 and 214 ofanvil 200 were not placed in contact with a second catalytic surface inthe presence of the same reactant gas. Portions 210, 212 and 214 werethen separated evaluated for the catalytic activity that occurred ateach individual portion. Anvil assembly 110 thus possesses anarrangement and geometry that provides for differential comparison ofthe “struck” (e.g., portion 212) and “unstruck” (e.g., portions 210,214) areas of anvil 200 while exposing all areas essentially identicalconditions. Differences in catalytic activity between “struck” and“unstruck” areas of anvil 200 may then, with allowance for the clearancetimes of reactant/product in the piping runs and suitable correction forany differences in total catalyst surface are owing to the intermittentpresence of the additional area of the striker in zone 212, beattributed solely to the contacting effects of, for example, the strikeron the anvil.

FIGS. 15A-C show various views of striker assembly 120, which ispositioned directly over anvil assembly 110 in SAT apparatus 100.

As shown in FIG. 15A, striker post 300 is connected to an assemblycomprising foil suspension strips 320 and 322, foil frame 310, andconnector rod 330. Connector rod 330 is further connected to actuator130, as shown in FIG. 13, which controls movement of striker post 300via the actuating foil mechanism, wherein foil strips 320 and 322oscillate as directed by actuator 130. Foil frame 310 is 18 mm thick andis precisely ground flat and parallel to allow proper clamping of foilsuspension strips 320 and 322. Foil suspension strips 320 and 322 andfoil frame 310 are made of X-750 material, and each have a differentthickness to ensure that their resonant frequencies differsignificantly. For example, foil suspension strip 322 is 0.001″ thickand foil suspension strip 320 is 0.002″ thick. Clamp assembly 340 and342 are constructed to have smooth surfaces in order to uniformlydistribute force across foil suspension strips 320 and 322 and tosolidly anchor foil suspension strips 320 and 322, which are tensionedin a setup fixture to 11 grams force. Spacer 341 is finished to have asmooth surface such that it contacts foil strip 320 uniformly, andscrews 343 are self-leveling. Actuator 130 directs oscillation of foilsuspension strips 320 and 322 via connector rod 330 such that strikerpost 300 moves in a direction 350 toward the anvil 200. Foil frame 310may be moved vertically via rotational mount 360.

FIG. 15C shows a close-up view of striker post 300 and striker 301,which was attached via brazing to a bottom surface of striker post 300such that striker 301 can contact anvil 200. The striker post 300 andthe anvil insert 201 were fabricated of a 316L stainless steel,providing very flat and smooth surfaces to which the catalyst materialwas brazed. The mating surfaces of these carrier parts were tinned in alike manner, removing any excess solder with solder-wick. The catalystpieces (i.e., anvil 200, striker 301) were then easily fused to thecarrier parts with a minimal amount of solder, by fusing the twopre-tinned parts in the presence of a very small amount of a rosin flux.The 316L parts were tinned with 221C tin-silver solder using ahydrochloric acid-based flux sold by Lucas-Milhaupt for stainless steelwork (Handy Flux Type TEC). A thin (0.003″ thick) ribbon of this SnAgeutectic alloy solder was provided by Lucas-Milhaupt. These tinning andfusing operations were carried out using an electrical temperaturecontrolled laboratory hot-plate. The fluxes used were thoroughly removedafter each soldering operation and followed with a pure water wash andacetone rinse before use.

As described above, striker 301 is a small plate of catalytic material(e.g. a 3×3 mm plate of Pd in this example) attached to a bottom surfaceof striker post 300, such that striker 301 contacts anvil 200 whenstriker post 300 is lowered in the direction 350 (FIG. 15A). Theremovable striker post 300 is fabricated from 316L material, is 0.250″diameter and has a precisely placed notch 347 near the top end whichengages two spring loaded ball dent screws 349 that position strikerpost 300 within the striker assembly 120. As shown in FIGS. 15B-C,striker post 300 also comprises a 1/16″ dowel pin 302 and is drawnagainst a V-groove 353 in the bottom of foil clamp plate 303 to maintainproper alignment of striker 301.

In the example embodiment, the striker 301 contacts the anvil 200 onlyat portion 212 of the anvil 200, and does not contact portions 210 or214 of anvil 200. As shown in the experimental runs described more fullybelow, the portion of anvil 200 which is contacted by striker 300 (i.e.,portion 212), in the presence of reactant gas, exhibited enhancedcatalytic activity relative to portions 210 and 214. In some cases,catalytic activity may be increased by over 50%, over 75% or over 90%,relative to the unstruck portions 210 and 214.

The catalyst materials were attached to striker post 300 and anvilinsert 201 by a special brazing technique employing a eutectic solder.Eutectic solders have a specific temperature at which they melt andimmediately become fluid (i.e., they do not display a softening range asthey are heated). This property allows the brazing of a flat catalystmaterial to a flat carrier metal such that the capillary action of thefluid solder ensures precise parallel mating of the surfaces. A varietyof alloys exist within a workable temperature range. In some cases, aparticular proportion of gold and silicon can be eutectic at arelatively high temperature. The alloy selected for experimentsdescribed herein was pure tin with 3.5% silver, which melts at precisely221° C. The catalyst material strips were tinned only on the mating sidewith this eutectic solder. After tinning, the tinned layer of the solderwas minimized by scavenging the tinned surface with “solder-wick,” whichis a very fine copper braid about 3 mm wide, coated with a “rosin” typesolder flux. The scavenging of the solder was carried to the point wherethe solder film is bright, smooth, thin and shows no small lumps or highpoints. After tinning, the striker 301 was attached to striker post 300and the anvil 200 was attached to anvil insert 201 via brazing.

A four-port Valco (VICI) selector valve 504, was used to sample,sequentially each of the three anvil areas and the input gas stream fromportions 210, 212, and 214. This type of selector valve vents thenon-selected, un-sampled ports to a vacuum dump line thereby maintainingflow through the sampled port and unselected lines keeping the flowcurrent for when a sample is selected.

Inlet port 230 and outlet port 220 were connected to their correspondingfeed or Valco ports through 1/16 inch 316L Stainless Steel tubingcommonly used in chromatography equipment and sold by Valco as T100C40as cleaned internally electro-polished and sealed in one meter lengths.These tubes were bent by hand to shape them to position so that each setof three rear openings that connect a nozzle block firmly seat each tubeinto its shouldered 1/16 inch opening thereby smoothly connecting the0.040″ (1 mm) internal tube diameter to the nozzle path. Each nozzle waswire EDM machined into the nozzle block 230, 220 providing a smoothlaminar flow transition from the round 1 mm ID to the 1.0×3.1 mm widenozzle slot. Lateral movement of the EDM wire was used to shape thesmooth transition from round to the broad nozzle aperture.

The use of EDM machining (e.g., machining of high Nickel alloymaterials) often produces residual products due to the spark erosion ofthe metal, leaving a “white layer”. Such “white layers” may form whentypical cleaning operations are performed or aggressive chemistries areused, which may cause the apparatus to malfunction. In order formechanical and chemical tolerance to be preserved, precision surfacesshould be brought to size in bright metal cleanliness. Accordingly, manycomponents of the SAT system 100 were manufactured from a singleone-inch thick plate of X-750 High Nickel alloy material, which ischemically resistant. The Ni alloy was annealed in vacuum at 1800° F.and quenched slowly in argon to develop desired properties for thisapplication. X-750 is prone to work harden during machining, especiallydue to precipitation hardening within a 1000 to 1300° F. temperaturerange. Thus, cutting speeds and feeds were carefully managed to avoidwork hardening. Cobalt cutters at moderate cutting speed were used.After substantial machining of pre-annealed material a subsequent annealcycle was performed to preserve properties and provide stability. Insome cases, two or three anneal cycles are preferred. In some cases,X-750 High Nickel alloy material is fully annealed before beginning anymachining operations, and the “white layer” of the mill product isremoved to a depth of 0.015-0.025 inches.

The SAT enclosure 140 was heated in a controlled manner by fivecartridge heaters (not pictured) embedded in a ¾ inch thick AluminumHeat Transfer Plate (not illustrated) intimately attached by twelve ¼-2018-8 Stainless Steel screws (not illustrated) to the bottom of the base141 of enclosure 140. This enabled tests to be conducted at elevatedtemperatures up to 200° C. or higher in some cases. Both mating faces ofthese two parts were surface-ground flat to better than 3/10,000 inchflatness with surface finish roughness less than 50 micro-inch. Thesurfaces were very thinly coated before assembly with a finely powderedBoron Nitride lubricant sold by Omega engineering as HTRC compound. Thetwo parts were repeatedly slid against each other moving an inch or soto evenly distribute the compound to insure that all of the surface iswetted with the compound by reducing the sliding stroke gradually tojust a millimeter or so. The ¼-20 screws were Pan headed with thinstainless washers and stainless Bellville spring washers to allow forthermal expansion while maintaining the desired clamping force. Theywere seated in counter-bored recesses (0.585″ D) in the bottom of theHeat Transfer Plate and the clearance hole for the ¼-20 screws were oversized at 0.280″.

Several thermocouples (not pictured) provide readout of the temperatureof the anvil during operation. These and other thermocouples were usedas sensors to control a PID temperature controller (not pictured) thatpowered five ¼-inch diameter 250 Watt cartridge heaters (not pictured)(available from Omega Engineering as CIR-1042/120V) embedded evenlyacross the mid-line of the Heat Transfer Plate. These cartridges werealso coated with the HTRC thermal compound to fully couple the heat tothe plate. The mounting holes for the ¼ inch diameter heaters provides10 to 12 thousandth inch clearance before the compound is applied as theheaters are inserted. The PID controller operates a “zero-switching”solid-state relay that minimizes electrical noise production that mightinterfere with the electronic control system and data logging computer(not pictured) that are part of the overall SAT system. To providecompressive stability and low heat transfer to the aluminum main baseplate, a 3- 3/16 inch thick block of closed-cell glass foam (trade name“Foamglas” from Dow Corning) material (not pictured) was cut from largerpieces and was laminated top and bottom with a 1/32 inch thick aluminumsheet metal to avoid crumbling the material. The laminating wasperformed using a Dow Coming 736 High Temperature RTV Silicone sealantusing a thin layer to adhere the metal to the glass foam. The length at14-⅝″ was slightly less than the enclosure base length and the width was5- 5/16″, allowing clearance for the heat transfer plate locating andpositioning brackets. The SAT enclosure 140 thus was mounted to the cartso that it was separated from the cart by the Foamglas block.

Enclosure 140 is designed to contain a moderately pressurized gaseousatmosphere, some of which flows over the contacting catalyst materials.The enclosure 140 has the dimensions, 18″×5.5″×7.5″, with a one-inchthick metal base 141 and a welded metal frame 143 supporting five sidesthat form an enclosed volume of about 8.5 liters. The frame and basewere fabricated from X-750 material and all the fully annealed partswere welded together using type 80 filler rod and subsequently annealedagain before finish machining. Each frame end is formed of one inchthick 5.5″ by 7.5″ X-750 material. The ends are each closed by a ½-inchthick metal bulkhead flat ground plate 145, 147, of 316L material thathas penetrations for the input gases and the thermocouple sensors. Bothof these bulkhead plates are secured with 6 mm stainless DIN cap screwsand self leveling spherical washers (JERGENS stainless self aligningwashers) threaded to the tapped holes in the enclosure frame ends. VitonO-rings of ⅛-inch nominal diameter material in a groove in each bulkheadplate seal them to provide leak free operation. The top and the twosides employ thick (e.g., 9 mm) borosilicate plate glass windows 149(Schott Glass) that form a pressure sealed enclosure, using similarViton O-rings to seal the sides. These O-rings were fabricated byvulcanizing to size by a commercial vendor using a reference plate withall the required three different rectangular grooves milled into thisplate as a check on the proper dimensioning. The front glass window isremovable. The top of enclosure 140 also employs a borosilicate glasswindow and has a hole 151 located directly above the Alnico 8 magnet 330attached to the top of the striker carrier upper foil clamp plate 332. APIN link air-bearing assembly 132, the structure of which is shown ingreater detail in FIGS. 17A-C, is installed with sealing O-rings andsilicone rubber gaskets so that the 0.030″ diameter 316L wire link rod131 is freely moved by an electromagnetic drive system 130 positioneddirectly above it.

The electromagnetic drive system 130 is mounted on a ½ inch thick Boomplate (not pictured) (VPN) mounted vertically on a Mast (VRT) (notpictured) made from an aluminum heavy-weight 6″ wide channel that issolidly anchored by bolts to a mating thick mounting block (notpictured), also securely bolted to a 30-inch square ¾ inch thickaluminum horizontal main base plate (not pictured). This main mechanicalbase rests on several inflated bicycle tires (not pictured) forming aneffective isolation of low-level vibration from the cart equipment orbuilding structure-borne sources, reducing undefined and uncontrolledlevels of vibrating variation of contact force between the striker andthe anvil.

SAT General Test Protocol

As described above, the SAT system is composed of six basic sub-systems.

1) gas sources and regulators,

2) valves and gas flow controls,

3) SAT test enclosure,

4) Valco selector valve,

5) Agilent 5879 Mass Selective Detector

6) Data logging computer and striker drive control electronics

A test run begins with the front window of the enclosure 140 opened. Thebayonet connected internal magnet link 133 to the PIN header 132 isremoved to allow the foil frame 310 to be rotated upward via rotationalmount 360 exposing the striker post 301 so that it may be removed andreplaced by a desired striker/catalyst post and the corresponding anvilinsert 201 with its catalyst material similarly removed and replacedwith one desired for the test run. These parts were prepared prior tosetting up a test run.

After installing the desired striker 301 and anvil 200, the next stepwas to begin a break-in run of the new striker and anvil. A break-in runwas started by first selecting the number of strokes to be taken bystriker post 300. Typically, 3000 strokes were used with the systemnormally operating at 3 strokes per second. After the break-in run, theanvil insert 201 and striker post 200 were examined in the SEM withphoto data taken and an EDAX analysis taken. The insert and post werereturned to the SAT enclosure and the front glass side of the enclosure140 was reinstalled.

The gas flow conditions were then established for the test. For thepalladium catalyst material runs, zero grade pure nitrogen carrier gaswas used at a flow rate of 2.5 liters per minute into the main port ofthe enclosure 140. Methane reactant gas was fed to the inlets 142 at arate of one liter per minute. Prior to beginning the test gas run, thechamber and nozzles were fed pure helium gas for 20 minutes to clear alllines. The shutoff valve 503 between the output of the Valco selectorvalve 504 and MSD 502 was kept closed until pressure indicated on theoutput of the enclosure 140 read stable at more than 1.5 psi. Duringthis period of initial gas flow into the enclosure the MSD's internalcalibration spectrum test was run using the test substance injectorbuilt in to the MSD 502. After completion of this test, MSD 502 isallowed to pump down and, when stable, the shutoff valve is opened andthe test run was begun. Throughout the test run, the performance of MSD502 and temperature conditions were logged by the system computer. Afterstable gas flow is established, the temperature adjustment program wasstarted for set points desired for the temperature of the testoperation.

Test runs were conducted at various temperature levels and over variedtime periods as described more fully below. The test runs were performedat 3 strokes per second with a strike force of about 12 g. After eachrun, the striker 301 and anvil 200 were again examined by SEM and EDAXfor mechanical changes or other surface effects. Typically, noalterations were found.

As shown in the results data described below, generally, substantialincreases in catalyzed product abundance were observed in samples takenfrom the contacted area of anvil 200 (e.g., portion 212) relative to thetwo un-contacted areas of anvil 200 (e.g., portions 210 and 214). TheValco selector valve 504 was used to sample sequentially product gasfrom portions 210, 212, and 214 of anvil 200, as well as the input gasstream for portions 210, 212, and 214. For example, portion 210 wassampled first, portion 212 was sampled second, and portion 214 wassampled third. In some cases, “unstruck” portion 214 was sampled tooquickly after “struck” portion 212, and carryover material (e.g., excessproduct) was observed for “unstruck” portion 214. This anomaly wasconfirmed by reversing the rotation of selector valve 504, such thatportion 214 was sampled first, portion 212 was sampled second, andportion 210 was sampled third. As expected, when “unstruck” portion 210was sampled too quickly after “struck” portion 212, carryover material(e.g., excess product) was observed for “unstruck” portion 210. When alonger period of time was allowed for clearing lines between eachsampling, the carry over effects were largely reduced. The catalyticenhancement effects far exceeded carryover effects.

Test Example 6 Use of SAT Apparatus for Pd-Catalyzed Synthesis ofHydrocarbons from Methane Gas at 70° C.

The SAT apparatus described above was fitted with a 5″12″ Pd anvil and a3″×3″ Pd striker and the test run was performed generally as describedabove. In this example, the SAT apparatus was heated to 70° C., andmethane gas was fed into inlets 142 at a rate of one liter per minute.During the test run, the striker contacted the anvil at a rate of 3strokes per second with a strike force of about 12 g. Samples of thereactant gas from the “struck” portion and the “unstruck” portions ofthe anvil were fed into the mass spectrometer over various periods oftime to measure levels of product produced during the test run.

FIG. 18A shows the mass numbers (x axis) and abundance (y axis) ofspecies in the reactant gas for an “unstruck” portion of the anvil,sampled at various times (z axis) during the test run. The peaks havinga mass number of about 14 correspond to the methane starting material,while the peaks at about 30 mass number correspond to a higherhydrocarbon product. FIG. 18B shows the mass numbers (x axis) andabundance of species (y axis) in the product gas for the “struck”portion of the anvil, sampled at various times (z axis) during the testrun. Comparing FIG. 18A with 18B shows that the ratio of the productabundance to the methane starting material abundance for the “unstruck”portion of the anvil is substantially less than that for the “struck”portion of the anvil, indicating that the contact between the Pd anviland Pd striker substantially enhanced the catalytic reactivity of Pd inthe synthesis of higher hydrocarbons from methane at this temperature.

Test Example 7 Use of SAT Apparatus for Pd-Catalyzed Synthesis ofHydrocarbons from Methane Gas at 150° C.

This test run was conducted as described in Test Example 6, except thatthe SAT apparatus was heated to 150° C. during the test run.

FIG. 19A shows the mass numbers (x axis) and abundance (y axis) ofspecies in the reactant gas for an “unstruck” portion of the anvil,sampled at various times (z axis) during the test run. FIG. 19B showsthe mass numbers (x axis) and abundance of species (y axis) in theproduct gas for the “struck” portion of the anvil, sampled at varioustimes (z axis) during the test run. Comparing FIG. 19A with 19B showsthat the ratio of the product abundance to the methane starting materialabundance for the “unstruck” portion of the anvil is substantially lessthan that for the “struck” portion of the anvil, indicating that thecontact between the Pd anvil and Pd striker substantially enhanced thecatalytic reactivity of Pd in the synthesis of higher hydrocarbons frommethane at this temperature.

Test Example 8 Use of SAT Apparatus for Pd-Catalyzed Synthesis ofHydrocarbons from Methane Gas from 71° C. to 31° C.

This test run was conducted as described in Test Example 6, except thatthe test run began with the SAT apparatus heated to 71° C., and thetemperature was lowered to 31° C. over the course of the test run.

FIG. 20A shows the mass numbers (x axis) and abundance (y axis) ofspecies in the reactant gas for an “unstruck” portion of the anvil,sampled at various times (z axis) during the test run. FIG. 20B showsthe mass numbers (x axis) and abundance of species (y axis) in theproduct gas for the “struck” portion of the anvil, sampled at varioustimes (z axis) during the test run. Comparing FIG. 20A with 20B showsthat the ratio of the product abundance to the methane starting materialabundance for the “unstruck” portion of the anvil is substantially lessthan that for the “struck” portion of the anvil, indicating that thecontact between the Pd anvil and Pd striker substantially enhanced thecatalytic reactivity of Pd in the synthesis of higher hydrocarbons frommethane over this temperature range.

Test Example 9 Use of SAT Apparatus for Pd-Catalyzed Synthesis ofHydrocarbons from Methane Gas from 60° C. to 80° C.

This test run was conducted as described in Test Example 6, except thatthe test run began with the SAT apparatus heated to 60° C., and thetemperature was raised to 80° C. over the course of the test run.

FIG. 21A shows the mass numbers (x axis) and abundance (y axis) ofspecies in the reactant gas for an “unstruck” portion of the anvil,sampled at various times (z axis) during the test run. FIG. 21B showsthe mass numbers (x axis) and abundance of species (y axis) in theproduct gas for the “struck” portion of the anvil, sampled at varioustimes (z axis) during the test run. Comparing FIG. 21A with 21B showsthat the ratio of the product abundance to the methane starting materialabundance for the “unstruck” portion of the anvil is substantially lessthan that for the “struck” portion of the anvil, indicating that thecontact between the Pd anvil and Pd striker substantially enhanced thecatalytic reactivity of Pd in the synthesis of higher hydrocarbons frommethane over this temperature range.

Test Example 10 Use of SAT Apparatus for Pd-Catalyzed Synthesis ofHydrocarbons from Methane Gas from 30° C. to 92° C.

This test run was conducted as described in Test Example 6, except thatthe test run began with the SAT apparatus heated to 30° C., and thetemperature was raised to 92° C. over the course of the test run.

FIG. 22A shows the mass numbers (x axis) and abundance (y axis) ofspecies in the reactant gas for an “unstruck” portion of the anvil,sampled at various times (z axis) during the test run. FIG. 22B showsthe mass numbers (x axis) and abundance of species (y axis) in theproduct gas for the “struck” portion of the anvil, sampled at varioustimes (z axis) during the test run. Comparing FIG. 22A with 22B showsthat the ratio of the product abundance to the methane starting materialabundance for the “unstruck” portion of the anvil is substantially lessthan that for the “struck” portion of the anvil, indicating that thecontact between the Pd anvil and Pd striker substantially enhanced thecatalytic reactivity of Pd in the synthesis of higher hydrocarbons frommethane over this temperature range.

Test Example 1 Use of SAT Apparatus for Pd-Catalyzed Synthesis ofHydrocarbons from Methane Gas from 100° C. to 200° C.

This test run was conducted as described in Test Example 6, except thatthe test run began with the SAT apparatus heated to 100° C., and thetemperature was raised to 200° C. over the course of the test run.

FIG. 23A shows the mass numbers (x axis) and abundance (y axis) ofspecies in the reactant gas for an “unstruck” portion of the anvil,sampled at various times (z axis) during the test run. FIG. 23B showsthe mass numbers (x axis) and abundance of species (y axis) in theproduct gas for the “struck” portion of the anvil, sampled at varioustimes (z axis) during the test run. Comparing FIG. 23A with 23B showsthat the ratio of the product abundance to the methane starting materialabundance for the “unstruck” portion of the anvil is substantially lessthan that for the “struck” portion of the anvil, indicating that thecontact between the Pd anvil and Pd striker substantially enhanced thecatalytic reactivity of Pd in the synthesis of higher hydrocarbons frommethane over this temperature range.

Test Example 12 Use of SAT Apparatus for Pd-Catalyzed Synthesis ofHydrocarbons from Methane Gas from 85° C. to 40° C.

This test run was conducted as described in Test Example 6, except thatthe test run began with the SAT apparatus heated to 85° C., and thetemperature was lowered to 40° C. over the course of the test run.

FIG. 24A shows the mass numbers (x axis) and abundance (y axis) ofspecies in the reactant gas for an “unstruck” portion of the anvil,sampled at various times (z axis) during the test run. FIG. 24B showsthe mass numbers (x axis) and abundance of species (y axis) in theproduct gas for the “struck” portion of the anvil, sampled at varioustimes (z axis) during the test run. Comparing FIG. 24A with 24B showsthat the ratio of the product abundance to the methane starting materialabundance for the “unstruck” portion of the anvil is substantially lessthan that for the “struck” portion of the anvil, indicating that thecontact between the Pd anvil and Pd striker substantially enhanced thecatalytic reactivity of Pd in the synthesis of higher hydrocarbons frommethane over this temperature range.

Test Example 13 Use of SAT Apparatus for Pd-Catalyzed Synthesis ofHydrocarbons from Methane Gas from 24° C. to 130° C.

This test run was conducted as described in Test Example 6, except thatthe test run began with the SAT apparatus heated to 24° C., and thetemperature was raised to 130° C. over the course of the test run.

FIG. 25A shows the mass numbers (x axis) and abundance (y axis) ofspecies in the reactant gas for an “unstruck” portion of the anvil,sampled at various times (z axis) during the test run. FIG. 25B showsthe mass numbers (x axis) and abundance of species (y axis) in theproduct gas for the “struck” portion of the anvil, sampled at varioustimes (z axis) during the test run. Comparing FIG. 25A with 25B showsthat the ratio of the product abundance to the methane starting materialabundance for the “unstruck” portion of the anvil is substantially lessthan that for the “struck” portion of the anvil, indicating that thecontact between the Pd anvil and Pd striker substantially enhanced thecatalytic reactivity of Pd in the synthesis of higher hydrocarbons frommethane over this temperature range.

Test Example 14 Use of SAT Apparatus for Pd-Catalyzed Synthesis ofHydrocarbons from Methane Gas from 100° C. to 65° C.

This test run was conducted as described in Test Example 6, except thatthe test run began with the SAT apparatus heated to 100° C., and thetemperature was lowered to 65° C. over the course of the test run.

FIG. 26A shows the mass numbers (x axis) and abundance (y axis) ofspecies in the reactant gas for an “unstruck” portion of the anvil,sampled at various times (z axis) during the test run. FIG. 26B showsthe mass numbers (x axis) and abundance of species (y axis) in theproduct gas for the “struck” portion of the anvil, sampled at varioustimes (z axis) during the test run. Comparing FIG. 26A with 26B showsthat the ratio of the product abundance to the methane starting materialabundance for the “unstruck” portion of the anvil is substantially lessthan that for the “struck” portion of the anvil, indicating that thecontact between the Pd anvil and Pd striker substantially enhanced thecatalytic reactivity of Pd in the synthesis of higher hydrocarbons frommethane over this temperature range.

While several embodiments of the invention have been described andillustrated herein, those of ordinary skill in the art will readilyenvision a variety of other means and structures for performing thefunctions and/or obtaining the results or advantages described herein,and each of such variations, modifications and improvements is deemed tobe within the scope of the present invention. More generally, thoseskilled in the art would readily appreciate that all parameters,dimensions, materials, and configurations described herein are meant tobe exemplary and that actual parameters, dimensions, materials, andconfigurations will depend upon specific applications for which theteachings of the present invention are used. Those skilled in the artwill recognize, or be able to ascertain using no more than routineexperimentation, many equivalents to the specific embodiments of theinvention described herein. It is, therefore, to be understood that theforegoing embodiments are presented by way of example only and that,within the scope of the appended claims and equivalents thereto, theinvention may be practiced otherwise than as specifically described. Thepresent invention is directed to each individual feature, system,material and/or method described herein. In addition, any combination oftwo or more such features, systems, materials and/or methods, providedthat such features, systems, materials and/or methods are not mutuallyinconsistent, is included within the scope of the present invention.

In the claims (as well as in the specification above), all transitionalphrases or phrases of inclusion, such as “comprising,” “including,”“carrying,” “having,” “containing,” “composed of,” “made of,” “formedof,” “involving” and the like shall be interpreted to be open-ended,i.e., to mean “including but not limited to” and, therefore,encompassing the items listed thereafter and equivalents thereof as wellas additional items. Only the transitional phrases or phrases ofinclusion “consisting of” and “consisting essentially of” are to beinterpreted as closed or semi-closed phrases, respectively. Theindefinite articles “a” and “an,” as used herein in the specificationand in the claims, unless clearly indicated to the contrary, should beunderstood to mean “at least one.”

The phrase “and/or,” as used herein in the specification and in theclaims, should be understood to mean “either or both” of the elements soconjoined, i.e., elements that are conjunctively present in some casesand disjunctively present in other cases. Other elements may optionallybe present other than the elements specifically identified by the“and/or” clause, whether related or unrelated to those elementsspecifically identified. Thus, as a non-limiting example, a reference to“A and/or B” can refer, in one embodiment, to A only (optionallyincluding elements other than B); in another embodiment, to B only(optionally including elements other than A); in yet another embodiment,to both A and B (optionally including other elements); etc. As usedherein in the specification and in the claims, “or” should be understoodto have the same meaning as “and/or” as defined above. For example, whenseparating items in a list, “or” or “and/or” shall be interpreted asbeing inclusive, i.e., the inclusion of at least one, but also includingmore than one, of a number or list of elements, and, optionally,additional unlisted items. Only terms clearly indicated to the contrary,such as “only one of” or “exactly one of,” will refer to the inclusionof exactly one element of a number or list of elements. In general, theterm “or” as used herein shall only be interpreted as indicatingexclusive alternatives (i.e., “one or the other but not both”) whenpreceded by terms of exclusivity, such as “either,” “one of,” “only oneof,” or “exactly one of.”

As used herein in the specification and in the claims, the phrase “atleast one,” in reference to a list of one or more elements, should beunderstood, unless otherwise indicated, to mean at least one elementselected from any one or more of the elements in the list of elements,but not necessarily including at least one of each and every elementspecifically listed within the list of elements and not excluding anycombinations of elements in the list of elements. This definition alsoallows that elements may optionally be present other than the elementsspecifically identified within the list of elements that the phrase “atleast one” refers to, whether related or unrelated to those elementsspecifically identified. Thus, as a non-limiting example, “at least oneof A and B” (or, equivalently, “at least one of A or B,” or,equivalently “at least one of A and/or B”) can refer, in one embodiment,to at least one, optionally including more than one, A, with no Bpresent (and optionally including elements other than B); in anotherembodiment, to at least one, optionally including more than one, B, withno A present (and optionally including elements other than A); in yetanother embodiment, to at least one, optionally including more than one,A, and at least one, optionally including more than one, B (andoptionally including other elements); etc.

Any terms as used herein related to shape, orientation, and/or geometricrelationship of or between, for example, one or more articles,structures, forces, fields, flows, directions/trajectories, and/orsubcomponents thereof and/or combinations thereof and/or any othertangible or intangible elements not listed above amenable tocharacterization by such terms, unless otherwise defined or indicated,shall be understood to not require absolute conformance to amathematical definition of such term, but, rather, shall be understoodto indicate conformance to the mathematical definition of such term tothe extent possible for the subject matter so characterized as would beunderstood by one skilled in the art most closely related to suchsubject matter. Examples of such terms related to shape, orientation,and/or geometric relationship include, but are not limited to termsdescriptive of: shape—such as, round, square, circular/circle,rectangular/rectangle, triangular/triangle, cylindrical/cylinder,ellipitical/ellipse, (n)polygonal/(n)polygon, etc.; angularorientation—such as perpendicular, orthogonal, parallel, vertical,horizontal, collinear, etc.; contour and/or trajectory—such as,plane/planar, coplanar, hemispherical, semi-hemispherical, line/linear,hyperbolic, parabolic, flat, curved, straight, arcuate, sinusoidal,tangent/tangential, etc.; direction—such as, north, south, east, west,etc.; surface and/or bulk material properties and/or spatial/temporalresolution and/or distribution—such as, smooth, reflective, transparent,clear, opaque, rigid, impermeable, uniform(ly), inert, non-wettable,insoluble, steady, invariant, constant, homogeneous, etc.; as well asmany others that would be apparent to those skilled in the relevantarts. As one example, a fabricated article that would described hereinas being “square” would not require such article to have faces or sidesthat are perfectly planar or linear and that intersect at angles ofexactly 90 degrees (indeed, such an article can only exist as amathematical abstraction), but rather, the shape of such article shouldbe interpreted as approximating a “square,” as defined mathematically,to an extent typically achievable and achieved for the recitedfabrication technique as would be understood by those skilled in the artor as specifically described.

All references cited herein, including patents and publishedapplications, are incorporated herein by reference. In cases where thepresent specification and a document incorporated by reference and/orreferred to herein include conflicting disclosure, and/or inconsistentuse of terminology, and/or the incorporated/referenced documents use ordefine terms differently than they are used or defined in the presentspecification, the present specification shall control.

1. A catalytic reactor system, comprising: at least two catalyticobjects, each object having at least one surface complementary in shapeand/or contour to at least one surface on another of the catalyticobjects such that a projected contact area between two of the catalyticobjects is capable of being greater than 1% of a catalytically activetotal external contact surface area of the two contacting catalyticobjects; and a contact-inducing device configured and arranged torepeatedly bring complementary surfaces of the at least two catalyticobjects into contact with each other such that the a projected contactarea between two of the contacting catalytic objects is on averagegreater than 1% of the catalytically active total external contactsurface area of the two contacting catalytic objects.
 2. The catalyticreactor system as in claim 1, comprising at least two catalytic objectseach object having at least one surface complementary in shape and/orcontour to at least one surface on each other of the catalytic objectssuch that a projected contact area between any two of the catalyticobjects is capable of being greater than 1% of a catalytically activetotal external contact surface area of the two contacting catalyticobjects.
 3. The catalyst reactor system as in claim 1, wherein each ofthe two catalytic objects comprise at least one essentially planarsurface such that an essentially planar surface of a first catalyticobject is capable of contacting an essentially planar surface of asecond catalytic object.
 4. The catalyst reactor system as in claim 1,wherein the catalytic objects comprise a catalytically active materialcomprising a metal or metal alloy.
 5. The catalyst reactor system as inclaim 1, wherein the catalytic objects further comprise a supportmaterial coated with a catalytically active material.
 6. The catalystreactor system as in claim 5, wherein the support material is a ceramic.7. The catalyst reactor system as in claim 1, wherein the at least twocatalytic objects comprise discrete particles or pellets.
 8. Thecatalyst reactor system as in claim 1, wherein the catalytic objects areessentially non-porous.
 9. The catalyst reactor system as in claim 7,wherein the catalyst reactor system comprises a slurry bubble columnreactor and the contact-inducing device comprises a device configured togenerate fluid flow capable of suspending and/or agitating the discreteparticles or pellets.
 10. The catalyst reactor system as in claim 1,wherein the catalyst reactor system comprises a continuously stirredtank reactor and wherein the contact-inducing device comprises astirring device.
 11. The catalyst reactor system as in claim 1, whereinthe contact-inducing device comprises a mechanical apparatus comprisingor to which is attached at least one of the catalytic objects.
 12. Thecatalyst reactor system as in claim 7, wherein the discrete particles orpellets have a shape that is essentially a truncated icosahedron. 13.The catalyst reactor system as in claim 1, wherein at least one of thecatalytic objects has a shape that is essentially a cylinder.
 14. Thecatalyst reactor system as in claim 13, where a cross-section of thecylinder perpendicular to its longitudinal axis has a perimeter that isessentially polygonal.
 15. The catalyst reactor system as in claim 1,wherein at least one of the catalytic objects is configured as a gearhaving a plurality of gear teeth comprising a catalytic material. 16.The catalyst reactor system as claim 1, further comprising a reactorcomprising an inlet configured to allow a reactant to flow into thereactor and an outlet configured to allow a product to flow out of thereactor, wherein the catalytic objects are contained within the reactorsuch that the catalytic objects are exposed to the reactant.
 17. Thecatalyst reactor system as claim 1, wherein the complementary surface ofthe first catalytic object has a surface area that is larger than thesurface area of the complementary surface of the second catalyticobject, such that, when in contact with the second catalytic object, thecomplementary surface of the first catalytic object comprises a firstportion of its surface area that is in contact with the complementarysurface of the second catalytic object and at least a second portion ofsurface area that is not in contact with the complementary surface ofthe second catalytic object.
 18. The catalyst reactor system as claim17, wherein the first portion of surface area of the complementarysurface of the first catalytic object that is in contact with thecomplementary surface of the second catalytic object can be isolatedfrom the at least a second portion of surface area that is not incontact with the complementary surface of the second catalytic objectsuch that reactants and/or products in contact with the first portion ofsurface area can be sampled independently from reactants and/or productsin contact with the at a second portion of surface area.
 19. A methodfor performing a reaction catalyzed by a heterogeneous catalyst,comprising acts of: exposing at least two objects each object having atleast one surface complementary in shape and/or contour to at least onesurface on another of the objects, at least one of which objects is acatalytic object having a surface that is catalytically active, to anenvironment comprising a selected reactant, creating repeated contactbetween the objects such that a projected contact area betweencomplementary surfaces of two contacting objects is on average greaterthan 1% of a catalytically active total external contact surface area ofthe two contacting objects, allowing the predetermined reactant toundergo a chemical reaction at the at least one catalytically activesurface to produced a product.
 20. The method as in claim 19, whereineach of the objects is a catalytic object having a surface that iscatalytically active.
 21. The method as in claim 20, wherein each of thecatalytic objects comprises at least one essentially planar surfacehaving an area comprising at least about 1% of the catalytically activeexternal surface area of the object.
 22. The method as in claim 19,wherein the catalyst objects are immersed in the environment.
 23. Themethod as in claim 19, wherein the environment is a solution comprisingthe selected reactant.
 24. The method as in claim 19, wherein theenvironment is a gas comprising the selected reactant.
 25. The method asin claim 19, wherein the contact is recurring and transient.
 26. Themethod as in claim 19, wherein the contact causes at least a portion ofan external catalytically active surface area of the catalytic object tobecome regenerated.
 27. A catalytic object, comprising an externalsurface comprising a plurality of mosaic patches/facets wherein at leastone mosaic patch/facet meets an adjacent facet at an edge to form apredetermined three-dimensional shape, wherein at least one mosaicpatch/facet comprises a catalytically active material.
 28. The catalyticobject of claim 27, wherein an individual mosaic patch/facet has asurface area greater than 1% of the total external surface area of thecatalytic object.
 29. The catalytic object of claim 27, wherein eachmosaic patch/facet comprises a catalytically active material.
 30. Thecatalytic object of claim 27, wherein at least one mosaic patch/facet isessentially planar.
 31. The catalytic object of claim 30, wherein eachmosaic patch/facet is essentially planar.
 32. The catalytic object ofclaim 27, wherein the catalytically active material comprises a metal ormetal alloy.
 33. The catalytic object of claim 27, wherein thepredetermined three-dimensional shape is essentially a truncatedicosahedron.
 34. The catalytic object of claim 27, wherein thepredetermined three-dimensional shape is essentially a cylinder.
 35. Thecatalytic object of claim 27, wherein the predeterminedthree-dimensional shape is essentially in the form of gear teeth on agear.
 36. The catalytic object of claim 31, wherein the edge is rounded.37. The catalytic object of claim 27, further comprising a supportmaterial coated with the catalytically active material.
 38. Thecatalytic object of claim 27, wherein the support material is a ceramic.39. A catalytic reactor system, comprising a mechanical apparatusconstructed and arranged to intermittently create contact between acatalytically active surface of a catalyst object and a contact surfaceof a second object, such that a projected contact area on averagebetween the two objects is greater than 1% of the total external contactsurface area of the two contacting objects.
 40. The catalytic reactorsystem of claim 39, wherein the contact surface of the second object isa catalytically active surface.
 41. The catalytic reactor system ofclaim 39, wherein the mechanical apparatus comprises a motor.
 42. Thecatalytic reactor system of claim 41, wherein the mechanical apparatuscomprises a gear pump device.
 43. The catalytic reactor system of claim41, wherein the mechanical mechanism comprises a series of gear pumpdevices.
 44. The catalytic reactor system of claim 39, wherein themechanical apparatus comprises an anvil and a striker.
 45. A method forproducing catalytic action upon at least one reactant material,comprising: providing at least two catalytic objects, wherein thecatalytic objects each comprise a catalytically active material on atleast a portion of an external surface, exposing the catalytic objectsto an environment comprising the reactant material, producing motion ofthe catalyst objects sufficient to cause repeated frequent transientsurface to surface impacting contact events between external surfaceareas of the catalyst objects using a contact-inducing device, thecontact events each having on average a projected contact area largerthan 1% of the average total projected contact surface area of thecatalyst objects coming into contact during the contact event, andtransforming at least some reactant material into a product chemicallydifferent from the reactant material.
 46. The method according to claim45, wherein the repeated frequent transient surface to surface impactingcontact events progressively occur such that essentially all thecatalytically active external surface of the catalyst objects comes intocontact during the method.
 47. The method according to claim 45, whereinthe motion averages distribution of the contact events over essentiallyall the catalytically active exterior surfaces of all the objects. 48.The method according to claim 45, wherein the motion averagesdistribution of the contact events over a majority of the catalyticallyactive exterior surfaces of the objects.
 49. The method according toclaim 45, wherein the motion averages distribution of the contact eventsover limited portions of the external surfaces of the objects comprisingthe catalytically active surfaces.
 50. The method according to claim 45,wherein the catalytically active external surface of at least a portionof at least one catalytic object is segregated into mosaicpatches/facets, each mosaic patch/facet having an exterior surface areathat is substantially less than the total catalytically active externalsurface area of the at least one catalytic object that is segregatedinto mosaic patches/facets.
 51. The method according to claim 50,wherein a first mosaic patch/facet of the catalytic object that issegregated into mosaic patches/facets has composition of surfacematerial different from a second mosaic patch/facet on the same catalystobject.
 52. The method according to claim 51, wherein a first mosaicpatch/facet of a first catalytic object which is segregated into mosaicpatches/facets has composition of surface material different from asecond mosaic patch/facet on a second catalyst object which issegregated into mosaic patches/facets.
 53. The method according to claim45, wherein the aspect ratio of at least one catalytic object is lessthan about 1.05.
 54. The method according to claim 45, wherein theaspect ratios of each of the catalytic objects is between about 1.25 andabout 1.05.
 55. The method according to claim 45, wherein the aspectratio of at least one of the catalytic object is between 1.25 and 2.00.56. The method according to claim 45, wherein the aspect ratio of atleast one of the catalytic objects is between about 2.00 and about 3.00.57. The method according to claim 45, wherein the aspect ratio of atleast one of the catalytic object is greater than about 3.00.
 58. Themethod according to claim 45, wherein all the catalytic objects haveessentially the same shape and size.
 59. The method according to claim45, wherein all the catalytic objects have essentially the same shapebut differ by more than five percent from at least one other catalyticobject in size.
 60. The method according to claim 45, wherein theexternal surface of the catalytic objects comprise mosaicpatches/facets, and wherein at least a first and a second catalyticobjects have different essentially polyhedral shapes from each other.61. The method according to claim 60, wherein the external surface ofthe first catalytic object comprises a first number of mosaicpatches/facets while the external surface of the second catalytic objectcomprises a second number of facets.
 62. The method according to claim60, wherein the first catalytic object differs by more than about 5% insize from the second catalytic object.
 63. The method according to claim61, wherein the first catalytic object differs by more than about 5% insize from the second catalytic object.
 64. The method according to claim45, wherein a shape of the catalytic objects is substantially the sameas a truncated icosahedron having rounded edges joining adjacentessentially planar mosaic patches/facets, wherein the width of a roundededge, defining a minimum distance separating adjacent essentially planarmosaic patches/facets, does not exceed about 2% of the nominal overalldiameter of the truncated icosahedron.
 65. The method according to claim64, wherein the sizes of corresponding dimensions of any two catalystobjects are within 5% of each other.